Rotogravure printing process

ABSTRACT

Aqueous, low-viscosity, printing fluids containing a watersoluble, cationic, thermosetting resin and a water-soluble dye which is compatible with the resin in solution. These printing fluids are useful in high speed printing processes.

United States Patent Faessinger Apr. 29, 1975 ROTOGRAVURE PRINTINGPROCESS [56] References Cited [75] Inventor: Robert W. Faessinger,Media, Pa. UNITED STATES PATENTS 2,556,902 6/l965 Chambers et ul260/29.4 [73] Asslgnee' 23 Paper Company Ph'lddelpha 2,730,446 1/1956Hutchins 162/162 2,769,799 ll/l956 Swen et al. 260/294 22 Filed; M 41973 2,926.]54 2/1960 Keim 260/29.2 3,128,222 4/l964 Herschler et al.162/162 PP 357,348 3,275,605 9/1966 Eastes et al 260/70 Relatedpplication Data FOREIGN PATENTS OR APPLICATIONS [63] Continuation-impartof Scr. No. 619,210, Feb. 28, 912902 2 19 2 Unitcd Kingdom 1967, whichis a continuation-in-part of Ser. Nos. 424,221, Jun. 8, 1965, abandoned,and Ser. No. YE. M r Tillma 424,223, Jan. 8, 1965, abandoned, and Ser,No. 77" "f' 424,224, Jan. 8, 1965, abandoned, and Scr. N0. l- 424 225Jan 8 9 5 abundonc AIIUIVIC), Agent, or F1rmBacon & Thomas [52] US. Cl260/29.2 N; 8/7; 8/82; [57] ABSTRACT 8/85; 117/15; 117/38; 117/155;260/294 R; Aqueous, low-viscosity, printing fluids containing 21 260/39P; 260/70; 260/72 R; 260/72 N; water-soluble, cationic, thermosettingresin and 21 260/78 SC water-soluble dye which is compatible with theresin g gl g 2 in solution. These printing fluids are useful in high 1e0 re speed printing processes.

30 Claims, N0 Drawings ROTOGRAVURE PRINTING PROCESS CROSS REFERENCE TORELATED APPLICATIONS This application is a continuation-in-part of mycopending application Ser. No. 619,210, filed Feb. 28, 1967, which inturn is a continuation-in-part of my applications Ser. Nos. 424,221,424,223, 424,224 and 424,225, all of which were filed Jan. 8, 1965 andall of which are now abandoned. This application is also closely relatedto (1) copending application Ser. No. 671,490, filed Sept. 28, 1967,which is a continuationin-part of application Ser. No. 424,220, filedJan. 8, 1965 and now abandoned; (2) copending application Ser. No.671,546, filed Sept. 27, 1967, which is a continuation-in-part ofapplication Ser. No. 424,226, filed Jan. 8, 1965 and now abandoned; (3)application Ser. No. 424,248, filed Jan. 8, 1965 and now abandoned; and(4) US. Pat. No. 3,389,108 to Smith et al. All of the applications andpatent l (2), (3) and (4) are assigned to the assignee of the presentinvention.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionpertains to novel printing fluids; more particularly, this inventionrelates to certain aqueous printing fluids which are mixtures ofself-curing, watersoluble, cationic thermosetting resins and particularwater-soluble dyes suitable for printing unsized webs at high printingvelocities, for example, up to about 5,000 ft./min. and over. Theprinted products obtained by printing with these novel printing fluidsare also within the purview of this invention.

2. Description of the Prior Art In most of prior-art rotogravureprocesses pigmented printing fluids containing high vapor pressuresolvent as carrier fluids have been used. These fluids contain dispersedparticulate matter of great hiding power. Particles dispersed withinthese fluids give the tinctorial strength needed for printing when thesefluids are deposited on the surface of the printed web and the solventremoved thereafter.

While the final print quality of these fluids is often excellent, theprocess possesses inherent limitations such.

as the velocity at which the web may be printed. as well as the rate ofsolvent removal from the pigmented fluids. Needless to say, the manydangers inherent in using high-vapor pressure solvents are considerable.Also, eliminating such a drying step if comparable or better economicresults can be obtained is obviously a desideratum.

Other prior-art shortcomings, in comparison with this process, are thelife span of the rotogravure roll or intaglio surface because thepigmented particulate materials abrade the roll surface in places ofcontact with another surface such as the printing nip, and doctorblades.

Still other shortcomings found in prior art rotogravure printing are thehigher viscosities of printing fluids. The viscosity, coupled with theabrasive nature of the fluid, illustrates why rotogravure rolls areshortlived in comparison with this process.

Additionally, the high viscosity of the prior-art fluids prevents theprinting process from running at high speeds. For example, at highspeeds the tackiness of the prior-art fluids would cause fiber pickingor removal from the web and also at still higher viscosities thistackiness causes the paper to wrap itself around the printing surface.This phenomenon is avoided by reducing the viscosity of the printingfluid by adding solvent Therefore, it is obvious that any change in oneproperty of the fluid will significantly alter other properties of thefluid if the nature of the prior art system is significantly changed toobtain improved results.

SUMMARY OF THE INVENTION It has now been found that a completely new andunobvious approach in printing fluids does overcome most of theprior-art shortcomings and allows the printing operations to be carriedout at web velocities up to about 5,000 ft./min. and higher or a webvelocity of about a mile per minute at a cost substantially lower thanachievable by any prior-art processes. The novel printing fluid suitablefor rotogravure printing at web velocities up to about 5,000 ft./min. inits generic sense comprises an aqueous solution of a cationic,thermosetting resin, a dye compatible with said resin, said dye andresin mixture having a stability of from about one hour in excess offour months and a transference value of from about 0 to about four, anda viscosity at 77F of less than about 20 cps.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention,cationic resin means any water soluble, polymeric resin speciespossessing one or more positive charges, such charges arising by virtueof the presence in the polymer backbone or pendantly organic ammonium,sulfonium or phosphonium groups. The cationic nature of such watersoluble polymeric resin species not only allows for greater polymeraffinity for cellulosic fibers but also provides the electro-staticsites necessary for potential salt formation with the dye molecules.

By thermosetting" property is meant the ability of a resin to becomehard, durable and insoluble at room temperature or more rapidly by theapplication of heat or some other form of energy. This property isusually associated with a crosslinking reaction of the individual resinmolecular species to form a three dimensional network of polymermolecules. In the case of this invention, the cross-linking processinvolves not only the polymeric resin species themselves, but in thepresence of a dye having resin-reactive groups the dye molecules becomea part of the resultant insoluble three dimensional network.

Solutions of thermosetting resins which are capable of cross-linking toan insoluble, durable state at room temperature upon solvent evaporationare sometimes referred to as.self-curing. However, this curing processcan be markedly accelerated by the application of heat and, in somecases, by the inclusion of an acidic catalyst.

The preferred resin solutions are those which are aqueous and contain acationic, thermosetting resin of the type previously described whichwill self-cure" with and in some cases without the aid of an acidiccatalyst to a hard, insoluble, durable state within about four weeks orless at room temperature.

The resin in solution must also exhibit non-dilatant viscositycharacteristics. For purposes of this invention, the describedcondensates are also limited by the viscosity considerations as set outherein.

The dyes which will find use in this invention must be water soluble. Inaddition, such dyes must be compatible with the resin in solution andmust be capable of reacting with the cellulose, with the resin or,preferably, with both during the resin curing process. It is obvious,hence, that the greater the reactivity of the dye molecules the lowerwill be the transference values of the colored imprint.

The water soluble dyes useful in the novel fluid are generally thosewith anionic characteristics, i.e., bearing an opposite change to theresin. Although the combination of a cationic resin and an anionicdyestuff is basically incompatible, this difficulty can be overcome byusing an amount of resin in excess of the stoichiometric ratio. Forexample, most water soluble, cationic, theremosetting resins may be madecompatible with direct acid and reactive dyes.

This stabilized solution, it is believed, in turn coacts by curing onthe fibers in the web and the degree of this reaction is measured by atransference value.

As there are an untold number of dyes and each dye, it has been found,reacts unpredictably vis-a-vis the particular resin, only a certainfamily of dyes will be operative in this process. However, since theconcept of using a particular water soluble thermosetting resin with aparticular dye is novel from the stability aspect as well as thetransfer value aspect, many dyes are eliminated on the basis of thefirst ground as well as on the second. The tests designed to delineatethe acceptable dyes from those failing in the instant fluids are set outbelow and fully discussed. Again, it is stressed that not all dyes meetthe first two requirements and that predictability is impossible toestablish beforehand. Moreover, in order for the dye to be acceptable,it must be used in quantities such as will establish an acceptableprint. Again, this property relates to stability as the dye affects thefluid stability if the dye is present in considerable amounts. In otherwords, for each particular resin-dye combination a direct relationshipexists between fluid stability and the ratio of resin non-volatilesolids (N.V.S.) to dye, i.e., stability is adversely affected as theresin to dye ratio decreases.

Obviously, the particular resin must be carefully selected, but it isequally important that a proper dye is obtained. This dye may wash outof the resin if it is of less than the proper reactivity. Again, theresult will be high transference values giving poor printed products.

Other reasons why the self-curing resin and dye solution must bespecifically selected are further discussed herein. In other words,besides the properties demanded because of the above disclosed reasons,additional properties described herein must be possessed by the resinsbefore these qualify for the present purpose.

In order to delineate the class of resins acceptable in the presentinvention it has been necessary to develop standards which will measurethe resin reactivity as well as the coreactivity of resin and dye. Ascan be well imagined, the present invention falls in an area where lackof prior art standards have resulted in a vacuum of acceptable standardsor measure, which will illustrate the present invention in an acceptablefashion. Thus, the present generic fluid concept involves a. adefinition of the useful resins b. a definition of a standard with whicha useful resin is compared c. a definition of the resin-dye system whichwill cover the generic concept, and

d. a delineation of the physical properties of these fluids as theseproperties further limit the acceptable resin-dye system. percent.

For the purpose of the present invention the useful resins are thoseresins which are cationic, water soluble, and thermosetting; the mostuseful resins being those resins which are capable of thermosetting atroom temperature within at least four weeks.

An alternative requirement of the resin is that it may be cured in ashorter time, i.e., it may be cured by application of heat. However,self-curing resins are the preferred kind. In general heat curing shouldbe accomplished at temperatures below 350F.

Besides the above properties which are necessary to establish whether auseful resin is suitable as a component for printing purposes, otherproperties are equally necessary for other reasons. Obviously, theadditional properties further limit the above class and eliminate someof the resins.

An important limit is the transference value of the resin-dye system.This transference value as further described herein is based on the factthat it represents the coaction of the resin-fiber-dye system. The exactchemical nature of the resin-dye-fiber system is unknown and for thisreason this arbitrary standard has been defined to test theresin-dye-fiber coaction in order to determine the acceptableresin-dye.solutions. This test embraces the defining of acceptable dyesin proper concentrations in the resin solution in order to obtainacceptable prints.

Finally, the resin-dye solutions must meet certain physical tests beforethese solutions may be used for printing purposes in the present processas defined herein.

Physical limits necessary to delineate the acceptable fluids are: 1viscosity, (2) lack of change of viscosity such as due to change inshearing rate, (3) surface tension, and (4) free from particulatecontamination and pigmented particles.

For example, in order to obtain a certain transference value with acertain dye an excess amount of resin may have to be used, this amountof resin may in turn be in excess of the viscosity constraint.(Conversely, the viscosity constraint may be satisfied with the properamount of resin but an inordinate amount of dye may have to be used withthe particular resin and thus the solution may fail because of theresin-dye coaction, i.e., a chemical reaction.)

An example of suitable resin compositions is disclosed in US.application, Ser. No. 318,493, filed Oct. 24, 1963. These resincompositions are prepared by reacting:

a. A compound selected from at least one member of the group consistingof amino-carboxylic acids of the formula H2N-R-C- OH and lactams of theformula wherein R is a divalent radical selected from the groupconsisting of saturated and unsaturated carbon atom chains of from 2 to20 carbon atoms, alicyclic radicals; and aromatic radicals; and R is analiphatic chain of from 4 to 18 carbon atoms;

b. A compound selected from at least one member of the group consistingof dibasic acid of the formula.

wherein R is a divalent radical selected from the group consisting ofsaturated 1 to 20 carbon atom radicals, unsaturated 2 to 20 carbon atomradicals, alicyclic radicals, aromatic radicals, and the esters andanhydrides of these acids;

c. at least one polyalkylene polyamine compound of the formula HN-(RNH),,H wherein R is an alkylene group of from 2 to 8 atoms and n isan integer of from about 1 to 5, provided that at least 50 percent ofthe polyamine compound is where n is greater than one; the above (a),(b) and (c) components on mole basis in the reaction mixture being offrom about 0.1: 1 0:09 to about 1.0: :13 respectively; the reactionbeing carried out at a temperature of from about 140C to about 230C fora time sufficient to achieve a viscosity of about A to X onGardner-Holdt scale at about 40 percent solid concentration in theaqueous reaction solution and 25C; further reacting the obtainedcondensation product with about 0.8 to about 1.5 moles of a crosslinkingagent per mole of reactive amine groups, said crosslinking member beingselected from at least one member of the group consisting of1,3-dichloropropanol, epichlorohydrin, dichloroethylene, dichlorobutene,divinylsulfone, methylene bisacrylamide, diallylamine, glyoxal,crotonaldehyde, divinylether, glycidylaldehyde and diglycidylether at atemperature of from about 25C to about 90C until the resulting producthas a viscosity of about A to T on Gardner-Holdt scale at about 10percent solids and at 25C, and stopping the reaction by adjusting the pHto about 4 to 5.

Another class of resin compositions different in physical and chemicalproperties from the previous resins but suitable to illustrate inanother aspect the novel printing fluid are illustrated in U.S.application, Ser. No. 396,698, filed Sept. 15, 1964.

The resins are prepared by reacting:

a. at least one member of the group consisting of a saturated aliphaticdicarboxylic acid having from 4 to 6 carbon atoms, diglycolic acid anddithioglycolic acid, with b. at least one member of the group consistingof a polyalkylene polyamine of the formula where R is an alkylene groupof 2 to 4 carbon atoms and n is an integer from 2 to 5, saidpolyalkylene polyamine and said dicarboxylic acid being reacted in amole ratio of from about 09:10 to about 1.15:1.0 in an aqueous medium ata temperature of i from about 160C to about 210C;

c. converting by means of an inorganic acid the polyaminopolyamidereaction product from steps (a) and (b) to an inorganic acid saltthereof;

(1. reacting saidsalt with an alkali cyanate in an aqueous solution toform a polyureide derivative, said cyanate being selected from at leastone member of the group consisting of lithium cyanate, sodium cyanate,potassium thiocyanate, said alkali metal cyanate being reacted with saidpolyaminopolyamide in mole ratios from about 0.8: 1.2 moles of thecyanate per mole of reactive amine, at a temperature of from about 50Cto about C;

. reacting the preceding product with an aldehyde selected from, atleast one member of the class consisting of formaldehyde,paraformaldehyde and trioxane, said aldehyde being present in an amountsuch that it is equivalent to from 1:1 to about 3: l at a temperature offrom about 60C to about C.

Another class of resins which is useful in this invention is a class ofcationic, water soluble, thermosetting resins which are prepared byreacting (a) urea (b) alkylene polyamine (c) formaldehyde and (d) atleast one member of the group consisting of thiourea, dicyandimide,guanidine and an amino triazine, said reaction being modified if desiredby adding to'it after gellation of the reaction mixture a viscositylowering reacting agent of a certain class and continuing repeatedly togellation stage said reaction resin. It is understood, though, that thereaction product obtained without the repeated viscosity loweringadditive is equally acceptable and useful. In cases where a viscositylowering additive has been employed, the product is a more desirablespecies. All the resins obtained by condensation of (a), (b), (c) and(d) are within the purview of this invention, since the viscositylimitation which is placed on the dye-resin mixture as one factor inthis invention delineates the acceptable from the unacceptable resins.

In further describing the above resins, these can be classified asmodifications of urea, alkylene polyamine and formaldehyde where part ofthe urea component has been replaced by other amine components such asamino triazines and the reaction is carried out in a specific way if itis desired to obtain a more efficacious product.

As mentioned before, urea is a component in the reaction. Alkylenepolyamine is another component and it may be conveniently represented bythe formula H N(C,,H ,,HN),H where x is 1 to 4 and n is 2 or 3. As thepartially urea replacing component the following groups of compounds areused: aminotriazines such as melamines (preferred) ammeline,formoguanamine, acetoguanamine, propionoguanamine, 4N-methyl 2acetoguanamine, 4N ethyl 2 acetoguanamines, etc., thioureas,dicyandiamide and guanidine.

The gelation preventing condensation reaction extending viscositylowering agents are water-soluble, non-ionic aliphatic compounds ormixtures thereof such as formaldehyde, paraformaldehyde, methyl alcohol,ethylalcohol, normal propyl alcohol, ethylalcohol, normal propylalcohol, isopropyl alcohol, tertiary butyl alcohol, aliphatic polyols,such as ethylene glycol, glyerine, diethylene glycols, triethyleneglycols, glucose as well as other non-ionic compounds such as furfurylalcohol, dimethylsulfoxide, dimethy-formamide, etc. Preparations of theabove resins with and without the viscosity lowering additive maybeunderstood by reference to U.S. Pat. Nos. 2,826,500, 2,856,314,2,902,472 and 3,223,513. The above patent disclosures are incorporatedin the present application to avoid an undue length of thisspecification.

Another class of resins which is useful in this invention is a class ofcationic, water soluble, thermosetting resins which are prepared byreacting (a) dibasic acid (b) alkylene polyamine with or without aglycol (c) epichlorohydrin or diglycidylether and in case of anunsaturated acid, the resin may be further reacted with an ethenoidcompound resin.

Dibasic acids or polybasic acids suitable in preparing these resinswhich are useful in the novel printing fluids of this invention arethose described in U.S. Patents 3,086,961, 2,926,154 and 2,926,l 16.These are in general of the formula HOOCR-COOH and are dibasic acids offrom C to C carbon atoms where R can be a saturated aliphatic moietysuch as in a diglycolic acid, and aliphatic hydrocarbon moiety such asin adipic acid, alicyclic acids moiety and aromatic moiety. Polybasicaromatic acids and acids where R is an unsaturated aliphatic hydrocarbonmoiety are also disclosed in British Pat. No. 917,254. All of the abovepatent disclosures are incorporated in the present specification toavoid undue duplication of material.

Polyamines of the alkylene polyamine disclosed in U.S. Pat. Nos.3,086,961, 2,926,154 and 2,926,116 are type represented by the followingformula:

Y is H and C,,,H ,,,NH

m is an integer from 2 to 4 p is an integer from 1 to 4 Alkylene glycolssuitable for reacting with the polybasic acid, alkylene polyamide arerepresented by the following formula:

g is an integer of from to 6 and m is an integer from 2 to 4.

These glycols are further described in U.S. Pat. No. 3,086,961.

As a crosslinking agent after either the polybasic acid and alkylenepolyamine have been reacted or after the polybasic acid, alkylenepolyamine and glycol have been reacted are halohydrins such asepichlorohydrin. Other crosslinking agents are alpha, omegadichloroalkylenes and other similar agents.

1f the polybasic acids are unsaturated these may be further reacted withethenoid compounds such as vinylacetate, esters of acrylic andmethacrylic acid, etc. Products of this nature are illustrated inBritish Pat. No. 917,254.

Another class of resins which is useful in this invention are thecationic ureaformaldehyde resins, prepared with or without following thesequential condensation procedure as described in British Pat. No.912,902. The resins of this class are obtained by a process of makingcationic, amine-modified, urea formaldehyde resins by the acidcondensation of a reaction mixture of urea, formaldehyde and at leastone polyalkylene polyamine of the formula x being an integer from 1 toand n being 2 or 3.

1f the reaction mixture is susceptible of polymerization to a gellstage, this may be avoided by including a viscosity lowering additive inthe reaction mixture to inhibit gelation thereof. These additives arewater soluble, non-ionic, aliphatic compounds. As additive is introducedinto the reaction mixture at the time of incipient gelation thereofwhereupon the condensation reaction can be continued to the point ofincipient gelation. This procedure permits continuation of condensation,

and production of resins of altered physical and chemical properties,ordinarily prohibited by gelation of the usual reaction mixtures. Thus,in the production of the preferred resins the inclusion of awater-soluble, nonionic aliphatic compound which is hydroxylated inaqueous solution, such as formaldehyde, methyl alcohol, ethyl alcohol,normal propyl alcohol, isopropyl alcohol, tertiary butyl alcohol,aliphatic polyols, including ethylene glycol, glycerine, diethyleneglycol, triethylene glycol, gluscose, and other non-ionic compounds, forexample, furfuryl alcohol, in the urea-formaldehyde-polyalkylenepolyamine reaction mixture inhibits gelation thereof or lowers theviscosity of partially gelled reaction mixtures sufficiently so that thecondensation reaction and conversion to effective resin may be extended.Depending somewhat upon the amount of additive employed and itsapplication in increments, a repetitive cycle of incipient gelation,reduction in viscosity, incipient gelation, extends the condensationreaction to the point that the ultimate composition product is apreferred wet-strength paper resin.

However, it shall be understood that the ureaformaldehydeamine modifiedresins are in general prepared by a conventional condensation terminatedat a given viscosity, rather than by the sequential gelationdilutionreaction. Therefore, both types of resins within this class are withinthe purview of this invention.

Still further classes of resins which are useful in preparing printingfluids which are within the generic scope of this invention are thoseclasses of resins which are useful in preparing specific printing fluidsdisclosed and claimed in the following copending and relatedapplications: U.S. Ser. No. 424,220; U.S. Ser. No. 424,222; and U.S.Ser. No. 424,226; all of which were filed on Jan. 8, 1965. Thedisclosures of these applications are hereby incorporated in presentapplication by reference thereto.

In order to render the cationic resins acceptable for printing purposesthe resins may need to be modified by acidic catalysts compatible withthe dye-resin solutions. Generally, the urea-formaldehyde cationicresins, as well as the polyurea type resins, are used in conjunctionwith the acidic catalyst. Examples of such acid catalysts are aceticacid, lactic acid, glycolic acid, diglycolic acid, citric acid,phosphoric acid, hydrochloric acid, ammonium chloride, etc. Polyaminetype resins illustrated above are pH independent and do not requirecatalysts. However, some pH adjustment might be required with certaindyes for compatibility and stability purposes.

Further, to improve fluid stability, particularly at low resin-to-dyeratios, fluid additives are included; these are exemplified by compoundssuch as formaldehyde, methyl alcohol, glyoxal, glycols such asethylene/- glycol(low molecular-weight polyethylene glycol) andpropylene glycol, glycol ethers such as Cellosolve and Carbitol;formamide, dimethylformamide, polyvinyl pyrolidone, tetrahydrofurfurylalcohol, dimethyl sulfoxide, and the like compounds such as compoundswith hydroxy containing moieties or highly polar unreactive compounds,etc.

Urea may also be added to the present fluids for dye solubilizing andformaldehyde scavenging. If problems exist with fluid afflnity forgravure rolls, which are generally chrome plated, surface-active agentsmay be added. Examples of these are non-ionic surface-active agents suchas nonylphenoxypoly-(ethylenoxide) and others obtainable from AtlasChemical Corp. such as the Atoms, Atmul, and Tween series of non ionics.

This printing fluid, as further amplified herein, is suit-' able forrotogravure intaglio printing of papers having an absorbency time of upto 600 see/0.010 ml. of water. The more preferred papers have anabsorbency rate as depicted in the following table.

The tests described above are conducted under atmospheric conditionscontrolled to 75 i 2F and 60 i 2% RH.

Fluid stability at room temperature (77F.) is herein defined as theperiod of time intercurring between the manufacture of a fluid and theappearance of physicalchemical changes that would adversely affectoperabil- TABLE ABSORBENT PAPERS Most More Type of Paper PreferredPreferred Preferred Multi-Ply Toilet/Facial Tissues Basis Weightlb./rcam 9.2 10.7 7.5 l 1.5 5.0 15.0 Absorbency sec/0.10 ml. 10 0 l 0180 Single Ply Toilet Tissue Basis Weight lb./ream 1 1.5 14.0 9.0 16.07.0 20.0 Absorbency see./0.0l ml. 0 60 0 l2() 0 300 Single PlyTowel/Wiper Basis Weight IbJream 20.0 360 l [.0 40.0 l0.0 50.0Absorbency see/0.10 ml. 0 60 0 360 0 600 Multi-ply Towel/Wiper BasisWeight lb./ream 9.0 20.0 8.0 2L0 5 0 25.0 Absorbency sec/0. ml. 0 60 0300 0 600 Single Ply Napkin Basis Weight lb./ream 12.0 15.5 9.0 l9.0 6.025.0 Absorbency see./0.0l ml. 0 100 0 360 O 600 Multi-Ply Napkin BasisWeight lb./ream 9.7 11.2 7.0 15.0 5.0 20.0 Absorbency see/0.10 ml. 0 3000 600 0 600 Basis weight expressed in pounds per ream (lb/ream). A reamas used herein is 24 inches X 36 inches X 480 sheets or a total of 2,880square feet.

Absorbency is expressed in seconds as the time required for the paperspecimen to absorb a specified volume of distilled water. The area ofeach specimen (obtained from a retail unit) is to be no less than 9square inches, cut to 3 inches X 3 inches. The specimen to be testedwill be suspended in a suitable frame to provide a flat, undistortedsurface with no contact, on either side of the specimen, with any othersurface or material. With the specimen thus prepared, the specificvolume of water in a single drop will be lowered by appropriatelydivisioned pipette to the surface of the specimen. Timing begins as thewater drop touches the specimen and ends with complete absorptiondefined as the instant at which the water on the surfacefails to reflect light.

For Single Ply Tissue and/or Napkins: 0.01 ml H O For All Others: 0. [0ml H O Samples from each case will be from no less than 10 percent ofthe retail units contained therein. Each individual test will be theresult of three (3) drops/side, reporting the 6-drop coverage as theindividual test result. The average of these tests will represent theabsorbency.

ity. These changes usually take place over a period of time and thelimiting factors from the standpoint of fluid utilization are thefollowing:

A 25 percent change in fluid viscosity from the original value and adeparture from the initial onephase solution.

Stability is measured on an arbitrary scale defined for most preferredfluids as A, signifying a stability of one month or more, for apreferredfluids as B, signifying a stability of 1 week to a month, for useablefluids as C, the stability ranging from 1 hour to 1 week and forunacceptable fluids as O, the stability being 1 hour or less or completeincompatibility in fluid components.

Fluid stability as herein defined is also indicative of shelf life orstorage life. Storage life, as defined by the Packaging Institute in theGlossary of Packaging Terms, 2nd ed., Riverside Press, Essex Conn., 1955is the period of time during which a packaged product can be storedunder specific temperature conditions and remain suitable for use.Sometimes called shelf life.

Even if a proper amount of dye can be dissolved in the solution it maynot be acceptable because of the bleeding in water or transfer valuetest.

The novel printing fluids can also be cleaned which is hardly possiblewith thepigmented printing fluids since filtering or centrifugationwould remove pigment tinctorial material. This property of the novelfluid gives rise to a recirculating system as, in the case ofloosely-bonded absorbent papers, the paper dust and loose fibers must beremoved from the fluid in order not to overload the system withparticulate materials. Therefore, the need for a low-viscosity aqueoussolution is important as these solutions can be easily cleaned orseparated from impurities such as by centrifugation. This viscositycriterion is of importance because the impurities are removed bycleaning means such as those based upon differences in specific gravity.Consequently, dust-laden webs as well as looselybonded webs can beprinted by means of these fluids because the fluids are cleanable.

Transference, as previously mentioned, relates to the ability of theprinted area to resist water washing or bleeding after the resin hascured to the thermosetting state.

Transference solutions establishing the standard values for thedifferent resin dye mixtures and classifying acceptable fluids are givenbelow:

Transfer is herein defined as the amount of tinctorial material removedfrom the original colored area by the addition of distilled water andtransferred to either an unprinted area of the same substrate or ontoanother substrate when physical contact is established.

Transfer rating scale:

No noticeable transfer 1 Very slight (barely noticeable) transfer 2Slight transfer 3 Moderate transfer 4 Heavy transfer 5 Very heavytransfer The transfer rating scale is based on the intensity of thecolor removed when compared with the intensity of the original coloredarea.

Transfer rating is by definition 0 as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue 1 dye-stuff (DuPontPontamine Sky blue 68X) are dissolved in 50 ml. of distilled waterheated to 130F. and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30 percentN.V.S.), US. Pat. No. 2,699,435 (Example 2 thereof, appropriatelyadjusted for its N.V.S. content) Uformite 700 (Rohm & Haas) withagitation. Subsequently, 3 g. of NHqC] are added to the dye-resinsolution and mixing is continued until the catalyst is completelydissolved. Using a 100 microliter pipet, three-hundredths of one ml.(0.03 ml.) of fluid is placed on a No. 1 Whatman filter paper and dried(cured) for one hour in an oven at 230F. The colored portion of thefilter paper is then immersed for five seconds in distilled water, theexcess water is removed by contacting any absorbent medium, and finallythe damp test sample is sandwiched between two two-layer pads of No. lWhatman filter paper. A two-pound weight is placed on the top of thefilter pad and remains there for at least ten hours, after which timethe sample is removed and the two filter surfaces in contact with thetest sample upon examination exhibit no noticeable transfer.

Transfer rating is by definition l as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue 1 dye-stuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml. of distilled waterheated to 130F. and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30 percentN.V.S.), US. Pat. No. 2,699,435, Uformite 700 (Rohm & Haas) withagitation. Subsequently, 3 g. of NH Cl are added to the dye-resinsolution and mixing is continued until the catalyst is completelydissolved. Using a microliter pipet, three-hundredths of one ml. (0.03ml.) of fluid is placed on a No. l Whatman filter paper and dried(cured) for 10 minutes in an oven at 230F. The colored portion of thefilter paper is then immersed for five seconds in distilled water, theexcess water is removed by contacting any absorbent medium, and finallythe damp test sample is sandwiched between two two-layer pads of No. 1Whatman filter paper. A two-pound weight is placed on the top of thefilter pad and remains there at least ten hours after which time thesample is removed and the two filter surfaces in contact with the testsample upon examination exhibit a very slight (barely noticeable)transfer.

Transfer rating is by definition 2 as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue 1 dye-stuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml. of distilled waterheated to F. and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30 percentN.V.S.) US. Pat. No. 2,699,435, Uformite 700 (Rohm & Haas) withagitation. Subsequently, 0.5 g. of NH Cl is added to the dye-resinsolution and mixing is continued until the catalyst is completelydissolved. Using a 100 microliter pipet, three-hundredths of one ml.(0.03 ml.) of fluid is placed on a No. l Whatman filter paper and dried(cured) for 60 minutes in an oven at 230F. The colored portion of thefilter paper is then immersed for five seconds in distilled water, theexcess water is removed by contacting any absorbent medium, and finallythe damp test sample is sandwiched between two two-layer pads of No. lWhatman filter paper. A two-pound weight is placed on the top of thefilter pad and remains there for at least ten hours, after which timethe sample is removed and the two filter surfaces in contact with thetest sample upon examination exhibit a slight transfer.

Transfer rating is by definition 3 as a result of carrying out thefollowing experiment: 2 g. of CI. Direct Blue 1 dye-stuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml. of distilled waterheated to 130F. and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30 percentN.V.S.), US. Pat. No. 2,699,435, Uformite 700 (Rohm & Haas) withagitation. Subsequently, 0.5 g. of NH Cl is added to the dye-resinsolution and mixing is continued until the catalyst is completelydissolved. Using a 100 microliter pipet, three-hundredths of one ml.(0.03 ml) of fluid is placed on a No. l Whatman filter paper and dried(cured) for 30 minutes in an oven at 230F. The colored portion of thefilter paper is then immersed for five seconds in distilled water, theexcess water is removed by contacting any absorbent medium, and finallythe damp test sample is sandwiched between two two-layer pads of No. lWhatman filter paper. A two-pound weight is placed on the top of thefilter pad and remains there for at least ten hours, after which timethe sample is removed and the two filter surfaces in contact with thetest sample upon examination exhibit a moderate transfer.

Transfer rating is by definition 4 as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue 1 dye-stuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml. of distilled waterheated to 130F. and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30 percentN.V.S.), US. Pat. No. 2,699,435, Uformite 700 (Rhom & Haas) withagitation. Subsequently, 0.5 g. NH Cl is added to the dye-resin solutionand mixing is continued until the catalyst is completely dissolved.Using a 100 microliter pipet, three-hundredths of one ml. (0.03 ml.) offluid is placed on a No. l Whatman filter paper and dried (cured) for 15minutes in an oven at 230F. The colored portion of the filter paper isthen immersed for five seconds in distilled water, the excess water isremoved by contacting any absorbent medium, and finally the damp testsample is sandwiched between two two-layer pads of No. l Whatman filterpaper. A two-pound weight is placed on the top of the filter pad andremains there for at least ten hours, after which time the sample isremoved and the two filter surfaces in contact with the test sample uponexamination exhibit a heavy transfer.

Transfer rating is by definition as a result of carrying out thefollowing experiment: 2 g. of Cl. Direct Blue 1 dye-stuff (DuPontPontamine Sky Blue 6 BX) are dissolved in 50 ml. of distilled waterheated to 130F. and transferred into 50 g. ofpolyhydroxypolyalkylenepolyurea-formaldehyde condensate (30 percentN.V.S.), US. Pat. No. 2,699,435, Uformite 700 (Rohm & Haas) withagitation. Subsequently, the dye-resin solution pH is adjusted to 10 byaddition of 20 drops of saturated NaOH solution and mixed until thecatalyst is completely dissolved. Using a 100 microliter pipet,three-hundredths of one ml. (0.03 ml.) of fluid is placed on a No. 1Whatman filter paper and sample remains uncured (not oven dried). Thecolored portion of the filter paper is then immersed for five seconds indistilled water, the excess water is removed by contacting any absorbentmedium, and finally the damp test sample is sandwiched between twotwo-layer pads of No. l Whatman filter paper. A two-pound weight isplaced on the top of the filter pad and remains there for at least tenhours, after which time the sample is removed and the two filtersurfaces in contact with the test sample upon examination exhibit a veryheavy transfer.

For the process to be operative at the high-web velocities such asaround 5000 ft./min. the viscosity of the fluid must be kept withincertain limits. At lower web velocities the viscosity may be higher suchas about 20 cps., but again, a more viscous fluid picks up more fiberand may be harder to filter and for this reason is not desirable. Forpurposes of this process viscosities below cps are preferred. The morepreferred range of viscosity for the fluid is of from about 3 cps to 10cps while the most preferred range is about 3 cps to about 7 cps at 77F.

In the instant case procedure for determination of liquid viscosities bythe Cannon-Fenske Routine Viscometer was used. Equipment needed forviscosity determination includes a constant-temperature bath withthermometer, heating and cooling coils, thermostat, stirrer, a timer andthe proper size Cannon-Fenske Routine Viscometer tubes. Size 50 tube isrecommended for a range of 0.8 to 3.2 centistokes, size 100 tube for 3to 12 centistokes, size 150 tube for 7 to 28 centistokes and size 200tube for to 80 centistokes.

The bath temperature is maintained at 250C 1 01C. The viscosity incentipoises is then calculated by multiplying the centistoke viscosityby the liquid density at C. The liquid density at 25C is calculated bythe following equation: Density of liquid at 25C (sp.g. at tF) (dens.waterat 60F) (dens. water at 25C/dens. water at tF) (.00610) [(sp. g. attF)/(dens. water at tF)] The above procedure as employed herein isdiscussed by M. R. Cannon and M. R. Fenske in Ind. Eng. Chem., Anal,Ed.', 10,297 (1938).

In another aspect the present fluid differs from those of prior art,namely, surface tension. While most of the prior art fluids are designedwith low surface tension characteristics to allow the wetting of theroll by the viscous fluid, presently defined fluids are operable athigh-surface tension values because low viscosity fluid wets theintaglio surface at acceptable rates. Depending on the degree of surfacewetting the surface tension may be varied by adding minor amounts ofwetting agents to give the best results. The preferred values are below50 dynes/cm and below the surface value of pure water (72 dynes/cm). Anacceptable range is from about 30 dynes/cm to about 60 dynes/cm. Thesurface tension is measured by means of Cenco-duNouy tensiometer.

In comparing the print obtained by means of the prior art pigmentedrotogravure inks with the print obtained by the novel fluid thefollowing differences exist. The prior art inks are opaque, i.e., theyhave considerable hiding power (impervious to the rays of light). On theother hand, the present dyes are transparent although these may becolored. The color value adjustment in prior art is obtained by addingwhite pigment and coloring. In the present fluids it is performed bypreparing a different fluid with a different dye concentration. lnpracticing this invention, the white pigment is not needed and its placeis taken by the color of the substrate, i.e., the color of fibers whichare for the most part white for bleached pulp. Consequently a componentpreviously required in a rotogravure ink is now eliminated. Of course,the printing of colored base sheets necessitates the use of colors that,upon becoming deposited on the base sheets, will give the'needed color,e.g., a blue base sheet must be printed with yellow dye-resin solutionto obtain a green color.

Besides the above factors which contribute to the acceptance of thepresent fluids, the cost factor is an equally important considerationherein. For example, the cost as well as the necessity of grinding ofpigment is eliminated because no pigment is used in this process.Reproducibility of color is extremely good because of standardized dyesand standardized colors. uniformity of fluid concentration is easilymaintained even during very long runs as no large amounts of volatilesolvents are used which require constant adjustment. Needless to say,these advantages render the present fluid much less costly andespecially suitable for modern high speed mass production methods.

The following examples will serve further to illustrate the invention:

EXAMPLE 1 50 parts by weight of CH O 37 percent solution were added to50 parts water and 1.072 parts by weight of the acid dye Acid Blue 45,Erio Fast Cyanine S conc. Geigy, and 0.428 parts by weight of the directdye C.I. Direct Blue 86, Hilton Davis Turquoise, were dissolved in theabove solution with agitation and heating to approximately l40F. Theresulting solution was added slowly, with agitation to a second vesselcontaining parts by weight of (N.V.S. 3 l .8 percent), a melaminemodified, cationic amine urea-formaldehyde resin of the type describedin US. Pat. Nos. 2,826,500, 2,856,314, 2,902,472 and 3,223,513. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 6.7, N.V.S. 21.5 percent.specific gravity 1.086, viscosity 6.4 cps at 77F, surface tension 4l.8dynes/cm., stability better than 2 months.

The fluid was printed with a 19 inch wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-ply crepetissue, i.e., facial tissue. The paper had an attractive blue designimprinted thereon, and had a color transfer rating of after 4 weeks ofaging at room temperature.

EXAMPLE 2 50 parts by weight of 37 percent CH O solution were added to50 parts water and 1.818 parts by weight of the reactive dye DrimarineScarlet ZGL, C.l. Reactive Red 19, Sandoz, and 0.182 parts by weight ofthe reactive dye Drimarine Red Z-2B, C.l. Reactive Red 17, Sandoz, weredissolved in the above solution with agitation and heating toapproximately l40F. The resulting solution was added slowly, withagitation to a second vessel containing 100 parts by weight of melaminemodified resin described in Example l (N.V.S. =3l.8 percent). Theresulting solution was agitated for minutes.

The fluid had the following properties: pH- 6.9,N.V.S.-26.2 percent,specific gravity -1.1 14, viscosity 17.2 cps, surface tension 56.3dynes/cm., stability better than 2 months.

The fluid was printed with a 19 inch wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive reddesign imprinted thereon, and had a color transfer rating of 0 after 4weeks of aging at room temperature.

EXAMPLE 3 50 parts by weight of CH O 37 percent solution were added to50 parts water and 2.52 parts by weight of the reactive dye CibacronBrilliant Blue BR, C.1., Reactive Blue 5, Ciba, and 0.48 parts by weightof the reactive dye Cibacron Turquoise Blue G, C.l. Reactive Blue 7,Ciba, were dissolved in the above solution with agitation and heating toapproximately l40F. The resulting solution was added slowly withagitation to a second vessel containing 100 parts by weight (N.V.S. 31.8percent) of the resin as described in Example 1.

The fluid had the following properties: pH -6.8, N.V.S. 18.9 percent,specific gravity 1.088, viscosity 7.50 cps, surface tension 44.5,stability 2 months.

The fluid was printed with a 19 inch wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attactive bluedesign imprinted thereon and had a color transfer rating of 0 after 4weeks of aging at room temperature.

EXAMPLE 4 50 parts by weight of 37 percent CH O were added to 50 partswater and 3.92 parts by weight of the acid dye C.l. Acid Blue 127,Lanasyn Brilliant Blue GL, Sandoz, and 0.04 parts by weight of thedirect dye C.1. Direct Black 38, Pontamine Black ETP. DuPont, and 0.04parts by weight of the direct dye C.l. Direct Violet 9, Erie BrilliantViolet 200 percent were dissolved in the above solution with agitationand heating to approximately l40F. The resulting solution was addedslowly with agitation to a second vessel containing 100 parts by weight(N.V.S. 31.8 percent) of the resin described in Example 1.

The fluid had the following properties: pH 6.6, N.V.S. 18.5 percent,specific gravity. 1.090, viscosity 6.55 cps, surface tension 35.4dynes/cm., stability better than 2 months.

The fluid was printed with a 19 inch wide commercial type rotorgravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-p1y drycrepe tissue, i.e., facial tissue. The fluid was also printed with a 15inch wide laboratory rotogravure printing unit at speeds up to 240 fpmon soft, absorbent, 2-p1y dry crepe tissue, i.e., facial tissue. Thepapers had attractive blue design imprinted thereon, which prints hadcolor transfer ratings of 0 after 4 weeks of aging.

EXAMPLE 5 50 parts by weight of CH O (37 percent solution) were added to50 parts water. 4 parts by weight of the direct dye Pontamine BrilliantGreen GX, which consists of 86 percent CI. Direct Yellow 44 and 14percent CI. Direct Blue 1, DuPont, were dissolved in the above solutionwith agitation and heating to approximately l40F. The resulting solutionwas added slowly, with agitation to a second vessel containing 100 partsby weight (N.V.S. 31.8 percent) of the resin previously described inExample 1.

The fluid had the following properties: pH 7.0, N.V.S.-17.1 percent,specific gravity 1.088, viscosity- 6.04 cps, surface tension 51.0dynes/cm., stability 2 months.

The fluid was printed with a 19 inch wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-p1y drycrepe tissue, i.e., facial tissue. The paper had an attractive greendesign imprinted thereon, which print had a color transfer rating of 1after 4 weeks of aging.

EXAMPLE 6 50 parts by weight of 37 percent CH O were added to 50 partswater and 0.332 parts by weight of the direct dye, C.l. Direct Yellow50, Pontamine Fast Yellow RL, DuPont, and 0.668 parts by weight of thedirect dye C.I. Direct Brown 95, Pontamine Fast Brown NP, DuPont, weredissolved in the above solution with agitation and heating toapproximately l40F. The resulting solution was added slowly withagitation to a second vessel containing 100 parts by weight (N.V.S. 31.8

' percent) of the resin described in Example 1.

EXAMPLE 7 60 parts by weight of glyoxol (30 percent solution) were addedto 40 parts water. 3.33 parts by weight of the reactive dye CibacronBrilliant Blue BR and 0.67

parts by weight of the reactive dye Cibacron turquoise Blue G-E, C.l.Reactive Blue 7, were dissolved in the above solution with agitation andheating to approximately 140F. The resulting solution was added slowly,with agitation, to a second vessel containing 100 parts by weight(N.V.S. 32.0 percent) of the resin previously described in Example 1.The solution was aged for 23 days before use.

The fluid had the following properties: pH 5.9, N.V.S. 30.1 percent,specific gravity 1.146, viscosity 7.4 cps after 23 days of aging,surface tension 43.5 dynes/cm., stability 3 months. The fluid wasprinted with a 19 inch wide commercial type rotogravure printing unit atspeeds up to 3,000 fpm on soft, absorbent, 2-ply crepe tissue, i.e.,facial tissue. The paper had an attractive blue design imprintedthereon, which print had a color transfer rating of 3 after 4 weeks ofaging.

EXAMPLE 8 50 parts by weight of 37 percent CH O were added to 50 partswater. 1.6 parts by weight of the reactive dye Drimarine Scarlet ZGL,C.I. Reactive Red 19, Sandoz, and 0.32 parts by weight of the reactivedye Drimarine Red Z-2B, C.l. Reactive Red 17, Sandoz, 0.08 parts byweight of the reactive dye Cibacron Turquoise Blue G-E, Ciba, weredissolved in the above solution with agitation and heating toapproximately 140F. The resulting solution was added slowly, withagitation, to a second vessel containing 100 parts by weight (N.V.S.32.8 percent) of the resin previously described in Example 1. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH-6.6, specific gravity 1.088,viscosity 5.74 cps, surface tension 50.3, stability better than 2months.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., toilet tissue. The paper had an attractive reddesign imprinted thereon and had a color transfer rating of after 4weeks of aging.

EXAMPLE 9 50 parts by weight of CH O (37 percent solution) were added to50 parts water. 5.25 parts by weight of the reactive dye CibacronBrilliant Yellow 36, Ciba and 0.75 parts by weight of the reactive dyeCibacron Turquoise Blue G-E, C.l. reactive Blue 7, Ciba, were dissolvedin the above solution with agitation and heating to approximately 140F.The resulting solution was added slowly, with agitation, to a secondvessel containing 100 parts by weight of the resin previously describedin Example 1. (N.V.S. approximately 32 percent). The resulting solutionwas agitated for 15 minutes.

The fluid had the following properties: pH-6.8, specific gravity 1.096,viscosity 9.65 cps, surface tension 40.9 dynes/cm., stability 1 month.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., toilet tissue. The paper had an attractive greendesign imprinted thereon, which print had a color transfer rating of 0after 4 weeks of aging.

EXAMPLE 10 50 parts by weight of 37 percent CH O were added to 50 partswater. 1.8 parts by weight of the direct dye C.I. Direct yellow 50,Pontamine Fast Yellow RL, and 0.882 parts by weight of the reactive dyeDrimarine Red Z-2B, C.l. Reactive Red 17, Sandoz and 0.1372 parts byweight of the reactive dye Drimarine Scarlet ZGL, C'.l. Reactive Red 19,Sandoz, and 0.206 parts by weight of the reactive dye Cibacron Black RP,C.l. Reactive Black 3, Ciba, were dissolved in the above solution withagitation and heating to approximately 140F. The resulting solution wasadded slowly, with agitation, to a second vessel containing parts byweight (N.V.S. approximately 31.8 percent) of the resin previouslydescribed in Example 1. The resulting solution was agitated for 15minutes.

The fluid had the following properties: pH-6.8, specific gravity 1.088,viscosity 5.79 cps, surface tension 55.7 dynes/cm., stability betterthan 2 months.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., toilet tissue. The paper had an attractive yellowdesign imprinted thereon, which print had a color transfer rating of 0after 4 weeks of aging at room temperature.

EXAMPLE 1 l 50 parts by weight of CH O (37 percent solution) were addedto 50 parts water. 3 parts by weight of the acid dye C.l. Acid Blue 45,Anthraquinone Blue BN, and 0.8 parts by weight of the reactive dye C.l.Reactive Blue 5, Cibacron Brilliant Blue BR. ClBA, were dissolved in theabove solution with agitation and heating to approximately F. Theresulting solution was added slowly with agitation to a second vesselcontaining 100 parts by weight (N.V.S. approximately 32 percent) of theresin previously described in Example 1. The resulting solution wasagitated for 15 minutes.

The fluid had the following properties: pH-6.8, specific gravity 1.090,viscosity 6.98 cps, surface tension 38.2 dynes/cm, stability 2 months.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent 2-ply dry crepetissue, i.e., toilet tissue and facial tissue. The papers had attractiveblue designs imprinted thereon, which prints had color transfer ratingsof 2 after 4 weeks of aging.

EXAMPLE 12 50 parts by weight of 37 percent CH O were added to 100 partswater. 1 part by weight of the reactive dye. C.l. Reactive Blue 5,Cibacron Brilliant Blue BR, and 1 part by weight of the reactive dye, C.l. Reactive Blue 7, Cibacron Turquoise Blue G, Ciba, were dissolved inthe'above solution with agitation and heating to approximately 140F. Theresulting solution was added slowly with agitation to a second vesselcontaining 100 parts by weight (N.V.S. approximately 32.8 percent) ofthe resin previously described in Example 1. The resulting solution wasagitated for 15 minutes.

The fluid had the following properties: pl-l-6.6, specific gravity1.091, viscosity 6.94 cps, stability better than 2 months.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissues, i.e., facial tissue and toilet tissue. The papers hadattractive blue designs imprinted thereon, which prints had colortransfer ratings of 0 after 4 weeks of aging.

EXAMPLE 13 50 parts by weight of 37 percent CH O were added to 100 partswater. 2 parts by weight of the direct dye Pontamine Brilliant Green GX,which consists of 86 percent CI. Direct yellow 44 and 14 percent CI.Direct Blue 1, DuPont, were dissolved in the above solution withagitation and heating to approximately 140F. The resulting solution wasadded slowly with agitation to a second vessel containing 100 parts byweight (approximately N.V.S. 32 percent) of the resin previouslydescribed in Example 1. The resulting solution was agitated for 15minutes.

The fluid had the following properties: pH 6.9, stability 2 months. I

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive greendesign imprinted thereon, which print had a color transfer rating of 1after 4 weeks of aging.

EXAMPLE 14 50 parts by weight of 37 percent CH O were added to 100 partswater. 0.024 parts by weight of the direct dye C.l. Direct Black 38,Pontamine Black ETP, Du- Pont, and 0.616 parts by weight of the reactivedye Cibacron Red Brown G. Ciba, and 2.36 parts by weight of the reactivedye Cibacron Yellow R, C.I. Reactive Yellow 3, Ciba, were dissolved inthe above solution with agitation and heating to approximately 140F. Theresulting solution was added slowly with agitation to a second vesselcontaining 100 parts by weight (N.V.S. approximately 31.8 percent) ofthe resin previously described in Example 1. The resulting solution wasagitated for 15 minutes.

The fluid had the following properties: pH-6.85, specific gravity 1.086,viscosity 5.85 cps, stability more than 46 days.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive yellowdesign imprinted thereon, which print had a color transfer rating of 1after 4 weeks of aging.

EXAMPLE 15 50 parts by weight of CH O (37 percent solution) were addedto 50 parts water. 2 parts by weight of the direct dye C.l. Direct Red24, Pontamine Fast Scarlet 4 BA, were dissolved in the above solutionwith agitation and heating to approximately 140F. The resulting solutionwas added slowly with agitation to a second vessel containing 100 partsby weight (approximate N.V.S. 32 percent of the resin previouslydescribed in Example 1. The resulting solution was agitated for 15minutes.

The fluid had the following properties: pH 6.8, stability 2 months.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent 2-ply dry crepetissue, i.e., facial tissue. The paper had an attractive red designimprinted thereon, which print had a color transfer rating of after 4weeks of aging.

EXAMPLE 16 20 parts by weight of 37 percent CH O and 30 parts by weightof 40 percent glyoxal were added to 50 parts water. 2 parts by weight ofthe direct dye Pontamine Brilliant Green GR, DuPont, were dissolved inthe above solution with agitation and heating to approximately 140F. Theresulting solution was added slowly with agitation to a second vesselcontaining parts by weight (N.V.S. approximately 32 percent) of theresin previously described in Example 1. The resulting solution wasagitated for 15 minutes.

The fluid had the following properties: pH 6.3, specific gravity 1.107,viscosity 6.92 cps, surface tension, 54.5 dynes/cm., stability more than44 days.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit on soft, absorbent, 2-ply dry crepe tissue, i.e., toilettissue. The paper had an attractive green design imprinted thereon,which print had a color transfer rating of 1 after 4 weeks of aging atroom temperature.

EXAMPLE 17 60 parts by weight of glyoxal (40 percent solution) wereadded to 40 parts water. 2 parts by weight of the direct dye PontamineBrilliant Green GX, DuPont, were dissolved in the above solution withagitation and heating to approximately 140F. The resulting solution wasadded slowly with agitation to a second vessel containing 100 parts byweight (N.V.S. approximately 32 percent) of the resin previouslydescribed in Example 1. The resulting solution was agitated for 15minutes.

The fluid had the following properties: pH -6.l, specific gravity 1.136,viscosity 8.39 cps, surface tension 56.2, d.p.c., stability 2 months.

The fluid was printed with a 15 inch wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent 2-ply dry crepetissue, i.e., toilet tissue. The paper had an attractive green designimprinted thereon, which print had a color transfer rating of 2 after 4weeks of aging.

EXAMPLE 18 2.5 parts by weight of a reactive dye Drimarine Red Z-RL,C.l. Reactive Red 20, Sandoz, were dissolved in 50 parts by weight ofethylene glycol with agitation and heating to F. The resulting solutionwas added slowly with agitation to 50 parts by weight of the resinpreviously described in Example 1 and having a nonvolatile solidscontent of approximately 31.8 percent. The resulting solution wasagitated for 15 minutes and 3.5 parts by weight of lactic acid 85percent catalyst were slowly added.

The fluid had the following properties: pH-3.0, viscosity 6.60 cps,surface tension 43.7 d.p.c., stability 1 month.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-p1y dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 2 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 19 50 parts by weight of 37 percent CH O were added to 50 partsof water in a container equipped with an agitator and means for heating.1 part by weight of a direct dye, C.1. Direct Red 81, Pontamine Fast Red8 BLX, was dissolved in the CH O H O solution with agitation and heatingto 140F. The resulting solution was added slowly with agitation to 100parts by weight of the resin previously described in Example 1 andhaving a nonvolatile solids content of approximately 32 percent. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 5.4, stability.- months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e. facial tissue. The redimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i F).

EXAMPLE 20 50 parts by weight of 37 percent CH O were added to 50 partsof water in a container equipped with an agitator and means for heating.1.5 parts by weight of an acid dye, C.1. Acid Blue 45, AnthraquinoneBlue BN, Geigy, were dissolved in the CH O H O solution with agitationand heating to 100F. The resulting solution was added slowly withagitation to 100 parts by weight of the resin previously described inExample 1 and having a nonvolatile solids content of approximately 32percent. The resulting solution was agitated for minutes.

The fluid had the following properties: pH 6.5., stability more than 45days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F i 10F) EXAMPLE 21 50 parts by weight of 37 percent CH 0were added to 50 parts of water in a container equipped with an agitatorand means for heating. 1 part by weight of an acid dye, C.I. Acid Green3, Pontacyl Green BL. Du- Pont, was dissolved in the CH O H O solutionwith agitation and heating to 100F. The resulting solution was addedslowly with agitation to 100 parts by weight of the resin previouslydescribed in Example 1 and having a non-volatile solids content ofapproximately 32 percent. The resulting solution was agitated for 15minutes.

The fluid had the following properties: pH 3.9, stability 5 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The greenimprinted area had a transfer rating of 4 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 22 30 parts by weight of Hexylene Glycol were added to 70 partsof water in a container equipped with an agitator and means for heating.3.148 parts by weight of a reactive dye, Cibacron Yellow R, C.l.Reactive Yellow 3, Ciba and 0.820 parts by weight a reactive dye,Cibacron Red Brown G and 0.032 parts by weight of a direct dye, C.l.Direct Black 38, Pontamine Black ETP, were dissolved in hexylene glycolH O solution with agitation and heating to 140F. The resultingsolutionwas added slowly with agitation to 100 parts byweight of the resinpreviously described in Example 1 and having a nonvolatile solidscontent of approximately 32 percent. The resulting solution was agitatedfor 15 minutes.

The fluid had the following properties: pH 6.3., specific gravity 1.070,viscosity 12.0 cps, surface tension 37.1 dynes/cm., stability more than40 days.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 2 after 4 weeks of aging at roomtemperature (77F :t 10F).

EXAMPLE 23 40 parts by weight of propylene glycol U.S.P. and 10 parts 37percent CH O were added to 50 parts of water in a container equippedwith an agitator and means for heating. 3,148 parts by weight of areactive dye, Cibacron Yellow R, C]. Reactive Yellow 3, Ciba, and 0.820parts by weight of a reactive dye, Cibacron Brown G, Ciba, and 0.32parts by weight of a direct dye, C.l. Direct Black 38, Pontamine BlackETP, were dissolved in the CH O glycol solution with agitation andheating to 140F. The resulting solution was added slowly with agitationto 100 parts by weightoof the resin previously described in Example 1and having a nonvolatile solids content of approximately 32 percent. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH-6.8, specific gravity 1.092,viscosity 12.9 cps, stability 1 month.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent 2 ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 24 50 parts by weight of 37 percent CH O were added to 50 partsof water in a container equipped with an agitator and means for heating.2 parts by weight of a direct dye, Pontamine Brilliant Green GX, weredissolved in the CH O H O solution with agitation and heating to 140F.The resulting solution was added slowly with agitation to 100 parts byweight of the resin previously described in Example 1 and having anonvolatile solids content of approximately 32 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 6.8, viscosity 5.21 cps,stability more than 1 month.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The greenimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F 1- 10F).

EXAMPLE 25 30 partsby weight of hexylene glycol were added to parts ofwater in a container equipped with an agitator and means for heating. 4parts by weight of a direct a dye, Pontamine Brilliant Green GX, DuPont,were dissolved in the H O/glycol solution with agitation and heating to130F. The resulting solution was added slowly with agitation to parts byweight of the resin previously described in Example 1 and having anonvolatile solids content of approximately 32 percent. Theresultingsolution was agitated for 10 minutes.

The fluid had the following properties: pH 7.0, specific gravity 1.068,viscosity 10.6 cps, stability 2 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2ply dry crepe paper, i.e., facial tissue. The greenimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i F).

EXAMPLE 26 3.0 parts by weight of the reactive dye, C.l. Reactive Yellow2, Cibacron Brilliant Yellow 30, Ciba, and 1 parts by weight of thereactive dye C.l. Reactive Blue 7, Cibacron Turquoise Blue G, Ciba, weredissolved in 100 parts of water with agitation and heating toapproximately 140F. The resulting solution was added slowly withagitation to a second vessel containing 100 parts by weight of Kymene709, Hercules Powder Co. (N.V.S. non-volatile solids aproximately 25percent, aqueous resin solution of cationic, expoxidized polyamides ofpolycarboxylic acids. This resin is one of the class of resins of thetype set forth in U.S. Pat. Nos. 2.926,l16 and 2.926,154, the variantsof which are also described in British Pat. No. 917,254 and U.S. Pat.No. 3,086,961. The resulting solution was agitated for minutes.

The fluid had the following properties: pH 3.4., N. V.S. 16.3, specificgravity 1.053, viscosity 10.83 cps, surface tension 43.6, stability 60days.

The fluid was printed with a 10 inch wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive greendesign imprinted thereon, and had a color transfer rating of 1 after 4weeks of aging at room temperature.

EXAMPLE 27 1 part by weight of the direct dye, C.l. Direct 81, PontamineFast Red 8 BLX, DuPont, was dissolved in 100 parts of water withagitation and heating to approximately 140F. The resulting solution wasadded slowly with agitation to a second vessel containing 100 parts byweight of Kymene 557 resin and falling within the first two descriptionsdisclosed in the patents in Example l 10 percent N.V.S.). 1 part of theabove solution was diluted with 15 parts of water.

The fluid had the following properties: pH 8.15, viscosity 1.01 cps,surface tension 55.7 dynes/cm, stability 3 months.

The fluid was printed at 3,050 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., facial tissue. The paper had a pink design imprinted thereon,which print had a color transfer rating of 2 after 4 weeks of aging atroom temperature.

EXAMPLE 28 2 parts by weight of the direct dye, C.l., Direct Yellow 50,Pontamine Fast Yellow R.L., DuPont, was dissolved in 100 parts by weightof water with agitation and heating to approximately 140F. The resultingsolution was added slowly with agitation to a second vessel containing100 parts by weight of Kymene 557 (10 percent N.V.S.) resin.

The fluid had the following properties: pH 5.6, viscosity 2.10 cps,surface tension 61.5 dynes/cm, stability- 3 months.

The fluid was printed at 2,000 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent, single-ply wet crepetissue, i.e., paper towel stock. The paper had a yellow design imprintedthereon, which print had a color transfer rating of 0 after 4 weeks ofaging.

EXAMPLE 29 1 parts by weight of the direct dye, C.l. Direct Blue 1.Pontamine Sky Blue 6 BX, was dissolved in parts by weight of water withagitation and heating to approximately F. The resulting solution wasadded slowly with agitation to a second vessel containing 100 parts byweight of Kymene 557 (10 percent N.V.S.) resin. 1 part of the resultingsolution was diluted with 1.5 parts of water.

The fluid had the following properties: pH 5.1, stability 4 weeks.

The fluid was printed at 1,050 fpm on a 15 percent wide laboratoryrotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., facial tissue. The paper had a blue design imprinted thereon,which print had a color transfer rating of 0 after 4 weeks of aging.

EXAMPLE 30 1 part by weight of the direct dye, C.l. Direct Violet 47,Pontamine Fast Violet 4RL, DuPont, was dissolved in 100 parts by weightof water with agitation and heating to approximately 140F. The resultingsolution was added slowly with agitation to a second vessel containing100 parts by weight of Kymene 557 (10 percent N.V.S.) resin. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 5.2, viscosity 7.14 cps,stability better than 2 months.

The fluid was printed at 2,000 fpm on a 15 inches wide laboratoryrotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., facial tissue. The paper had an attractive violet design imprintedthereon and had a color transfer rating of 0 after 4 weeks of ag-EXAMPLE 31 1 part by weight of the direct dye, C.l. Direct Red 24,Pontamine Fast Scarlet 4BA, DuPont, was dissolved in 100 parts of weightof water with agitation and heating to approximately 140F. The resultingsolution was added slowly with agitation to a second vessel containing100 parts by weight of Kymene 557 (10 percent N.V.S.) resin. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 5.2, viscosity 7.22 cps,stabilitybetter than 2 months.

The fluid was printed at 2,150 fpm on a 15 inches wide laboratoryrotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., facial tissue, and l-ply wet crepe tissue, i.e., towel, at 300fpm. Attractive red designs imprinted thereon had color transfer ratingsof 0 after 4 weeks of aging.

EXAMPLE 32 1.6 parts by weight of the reactive dye, Drimarine ScarletZGL, C.l. Reactive Red 19, Sandoz, and 0.32 parts by weight of thereactive dye, Drimarine Red 28, Sandoz, 0.08 parts by weight of thereactive dye, C.l. Reactive Blue 7, Cibacron Turquoise Blue G-E, C.l.Reactive Blue 7, Ciba, were dissolved in 100 parts by weight of waterwith agitation and heating to approximately 140F. The resulting solutionwas added slowly with agitation to a second vessel containing 100 partsby weight of Kymene 709 (25 percent N.V.S.) resin. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 3.1, N.V.S. 13.9 percent,specific gravity 1.045, viscosity 14.6 cps, stability better than 2months.

The fluid was printed at 240 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., facial tissue. The paper had an attractive red design imprintedthereon, which print had a color transfer rating of after 4 weeks ofaging.

EXAMPLE 33 4.375 parts by weight of the reactive dye, Reactive Yellow 2,Cibacron Brilliant Yellow 3 G, Ciba, and 0.625 parts by weight of thereactive dye, Cibacron Turquoise Blue G-E, Reactive Blue 7, Ciba, weredissolved in 100 parts of water with agitation and heating toapproximately 140F. The resulting solution was added slowly withagitation to a second vessel containing 100 parts by weight of Kymene709 (25 percent N.V.S.) resin. The resulting solution was agitated forminutes.

The fluid had the following properties: pH 3.2, specific gravity 1.052,surface tension 44.9 dpc, stability -1 month.

The fluid was printed at 240 fpm on a 15 inch wide laboratoryrotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., facial tissue. The paper had an attractive green design imprintedthereon, which print had a color transfer rating of 0 after 4 weeks ofaging.

EXAMPLE 34 1.9304 parts by weight of the direct dye, C.l. Direct Yellow50, Pontamine Fast Yellow RL, DuPont and 0.0230 parts by weight of thereactive dye, Drimarine Red 28, Cl. Reactive Red 17, Sandoz, 0.0672parts by weight of the reactive dye, Drimarine Scarlet ZGL, C.l.Reactive Red 19, Sandoz, and 0.0154 parts by weight of the direct dye,C.l. Direct Black 38, Pontamine Black ETP, DuPont, were dissolved in 100parts by weight of water with agitation and heating to approximately140F. The resulting solution was added slowly with agitation to a secondvessel containing 100 parts by weight of Kymene 709 (N.V.S. 25 percent)resin. The resulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 3.5, speciflc gravity 1.046,viscosity 11.1 cps, surface tension 56.6 dynes/cm, stability 1 month.

The fluid was printed at speeds up to 240 fpm on a 15 inches widelaboratory rotogravure printing unit on soft, absorbent, 2-ply dry crepetissue, i.e., toilet tissue. The paper had an attractive yellow designimprinted thereon, and had a color transfer rating of 0 after 4 weeks ofaging.

EXAMPLE 35 0.8 parts by weight of the reactive dye, C.I. Reactive Blue7, Cibacron Turquoise Blue G-E, Ciba, and 3 parts by weight of the aciddye, C.l. Acid Blue 45, Anthraquinone Blue BN, DuPont, were dissolved in100 parts of water with agitation and heating to approximately 140F. Theresulting solution was added slowly with agitation to a second vesselcontaining 100 parts by weight of Kymene 709 (25 percent N.V.S.) resin.The resulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 3.2, specific gravity 1.050,viscosity 14.95 cps, stability 15 days.

The fluid was printed at speeds up to 240 fpm on a 15 inches widerotogravure printing unit on soft, absorbent, 2-ply dry crepe tissue,i.e., toilet tissue. The paper had an attractive blue design imprintedthereon, which print had a color transfer rating of 1 after 4 weeks ofaging.

EXAMPLE 36 1 part by weight of a direct dye, C.l. Direct Red 26,Pontamine Fast Scarlet 8BSN, DuPont, was dissolved in parts of H 0 withagitation and heating to F. The resulting solution was added slowly withagitation to 100 parts by weight of Kymene 557 resin having anonvolatile solids content of approximately 10 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 5.5, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F 1 10F).

EXAMPLE 37 1 part by weight of a direct dye, C.I. Direct Red 4,Pontamine Fast Scarlet G, DuPont, was dissolved in 100 parts of waterwith agitation and heating to 130F. The resulting solution was addedslowly with agitation to 100 parts by weight of Kymene 557 resin havinga nonvolatile solids content of approximately 10 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 5.7, stability 4 months.

The fluid was applied by hand-operated simulted rotogravure method onsoft, absorbent, 2-ply dry crepe paper, He, facial tissue. The redimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 38 1 part by weight of a direct dye, C.l. Direct Yellow 26,Pontamine Fast Yellow 5 GL, DuPont, was dissolved in 100 parts of waterwith agitation and heating to 130F. The resulting solution was addedslowly with agitation to 100 parts by weight of Kymene 557 resin havinga non-volatile solids content of approximately 10 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 5.5., stability 5 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 39 1 part by weight of an acid dye, C.l. Acid Yellow 3,Chinoline Yellow 0 Conc., Sandoz, was dissolved in 100 parts of waterwith agitation and heating to 130F. The resulting solution was addedslowly with agitation to 100 parts by weight of Kymene 557 resin havinga non-volatile solids content of approximately 10 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 5.2, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft absorbent, 2-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 4O 1 part by weight of a direct dye, C.l. Direct Green 26,Pyrazol Fast Green BL, Sandoz, was dissolved in 100 parts of water withagitation and heating to 130F. The resulting solution was added slowlywith agitation to 100 parts by weight of Kymene 709 resin having anonvolatile solids content of approximately 25 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 6.2, stability months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The greenimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F i F).

EXAMPLE 41 1 part by weight of an acid dye, C.l. Acid Green 3, AcidGreen 2 G conc., Sandoz, was dissolved in 100 parts of water withagitation and heating to 130F. The resulting solution was added slowlywith agitation to 100 parts by weight of Kymene 709 resin having anonvolatile solids content of approximately 25 percent. The resultingsolution was agitated for minutes.

The fluid had the following properties: ph-5.4, stability 3 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The greenimprinted area had a transfer rating of 3 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 42 1 part by weight of an acid dye, C.l. Acid Blue 1, Kiton PureBlue V Ex. Con., Ciba, was dissolved in 100 parts of water withagitation and heating to 130F. The resulting solution was added slowlywith agitation to 100 parts by weight of Kymene 557 resin anon-volatilesolids content of approximately 10 percent. The resulting solution wasagitated for 15 minutes.

The fluid had the following peoperties: pH 5.4, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 3 after 4 weeks of aging at roomtemperature (77F 1 10F).

Example 43 1 part by weight of a reactive dye, Drimarine Navy Z BGLp.a.f., C.I. Reactive Blue 8, Sandoz, was dissolved in 100 parts ofwater with agitation and heating to 130F. The resulting solution wasadded slowly with agitation to 100 parts by weight of Kymene 709 resinhaving a non-volatile solids content of approximately 25 percent. Theresulting solution was agitated for 15 minutes.

The fluid had the following properties: pH 3.6, stability 2 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F 1 10F).

EXAMPLE 44 1 part by weight of a direct dye, C.l. Direct Orange 51,Chlorantine Fast Orano LGL, Ciba, was dissolved in parts of water withagitation and heating to F. The resulting solution was added slowly withagitation to 100 parts by weight of Kymene 709 resin having anon-volatile solids content of approximately 25 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 5.1, stability 6 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The orangeimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 45 1 part by weight of an acid dye, C.l. Acid Orange 10, KitonFast Orange G conc., Ciba, was dissolved in 100 parts of water withagitation and heating to 130F. The resulting solution was added slowlywith agitation to 100 parts by weight of Kymene 557 resin having anonvolatile solids content of approximately 10 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH-5.4, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent 2-ply dry crepe paper, i.e., facial tissue. The orangeimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 46 1 part by weight of a direct dye, C.l. Direct Violet 47,Pontamine Fast Violet 4RL, DuPont, was dissolved in 100 parts of waterwith agitation and heating to 130F. The resulting solution was addedslowly with agitation to 100 parts by weight of Kymene 557 resin havinga non-volatile solids content of approximately 10 percent. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 5.0, stability 9 months.

The fluid was applied by a hand-operated rotogravure method on soft,absorbent 2-ply dry crepe paper, i.e., facial tissue. The violetimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 47 2 parts by weight of a direct dye, C.l. Direct Violet 47,Pontamine Fast Violet 4 RL, are added directly to 100 parts by weight ofKymene 709 resin (25 percent approximate N.V.S.) with agitation and heatto F. The dye-resin is mixed until solution is complete.

The fluid had the following properties: pH -2.8. stability better than 4months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply crepe paper, i.e., facial tissue. The violetimprinted area had a transfer rating of after 4 weeks of aging at roomtemperature (77F i F).

EXAMPLE 48 0.4 parts by weight of a reactive dye, C.1. Reactive Blue 7,Cibacron Turquoise Blue G-E, Ciba, and 1.5 parts by weight of an aciddye, C.1. Acid Blue 45, Anthraquinone Blue BN, DuPont, are addeddirectly to 100 parts by weight of Kymene 709 resin with agitation andheating to 140F. The dye-resin is mixed until solution is complete.

The fluid had the following properties: pH 3.1, stability 3 weeks.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply crepe paper, i.e., facial tissue. The flueimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F t 10F).

EXAMPLE 49 2 parts by weight of a direct dye, C.1. Direct Red 81,Pontamine fast Red 8BLX, DuPont, are added directly to 100 parts byweight of Kymene 709 (N.V.S. percent) with agitation and heat to 140F.The dye-resin is mixed until solution is complete.

The fluid had the following properties: pH 3.1, stability 2 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 3 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 50 33 parts by weight of 37 percent CH O solution were added to66 parts by weight of an aqueous, cationic, amine-modified,ureaformaldehyde resin solution of the type described in British Pat.No. 912,902 and Canadian Pat. No. 639,980, having a N.V.S. (Non-volatilesolids) of 32 percent (UFC-l 156). 0.4 parts by weight of the reactivedye C.1. Reactive Blue 1, Cibacron Turquoise Blue G-E, Ciba, and 1.5parts by weight'of the acid dye, C.l. Acid Blue 45, Anthraquinone BlueBN, DuPont, were dissolved in the above solution with agitation andheating to approximately 140F. The resulting solution was agitated for20 minutes and one part of Glacial Acetic Acid catalyst was slowlyadded. The fluid had the following properties: pH 5.1, N.V.S. 27.3percent, specific gravity 1.122, viscosity 7.197 cps, stability morethan 3 months.

The fluid was printed with a 19 inches wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-p1y drycrepe tissue, i.e., facial tissue. The paper had an attractive bluedesign imprinted thereon, which print had a color transfer rating of 3after 4 weeks of aging at room temperature.

EXAMPLE 5 1 33 parts by weight of 37 percent CH O were added to 66 partsby weight of the above described resin having a N.V.S. of 32 percent.0.8 parts by weight of the reactive dye Drimarine Scarlet 2-GL P.A.F.C.I. reaccosity 6.89 cps at 77F. surface tension 51 dynes/cm. I

at 77F., stability better than 3 months.

The fluid was printed with a 19 inches wide commericial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive pinkdesign imprinted thereon, which print had a color transfer rating of 0after 4 weeks of aging at room temperature.

EXAMPLE 52 33 parts by weight of 37 percent CH O were added to 66 partsby weight of the above described resin having a N.V.S. of 29.5 percent.0.2 parts by weight of the reactive dye C.I. Reactive Bluel, CibacronTurquoise Blue G-E, Ciba, 0.75 parts by weight of the acid dye, C.1.Acid Blue 45, Anthraquinone Blue BN, DuPont, were dissolved in the abovesolution with agitation and heating to approximately F. The resultingsolution was agitated for 15 minutes and 1 part of glacial acetic acidcatalyst was slowly added.

The fluid had the following properties: pH 5.1, N.V.S. 24.9, specificgravity 1.115, viscosity 5.66 cps, stability 3 months.

The fluid was printed with a 19 inches wide commercial type rotogravureprinting unit at speeds up to 3,000 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive bluedesign imprinted thereon, which print had a color transfer rating of 1after 4 weeks of aging.

EXAMPLE 53 33 parts by weight of 37 percent CH O were added to 66 partsby weight of the above described resin (UPC-1156) having a N.V.S. of 29percent. 1.75 parts by weight of the reactive dye C.1. Reactive Yellow2, Cibacron Brilliant Yellow 3G, Ciba, 0.25 parts by weight of thereactive dye C .X. Reactive Blue 7, Cibacron Turquoise Blue G. Ciba,were dissolved in the above solution with agitation and heating toapproximately 140F. The resulting solution was agitated for 15 minutesand 1 part of acetic acid (glacial) catalyst was slowly added.

The fluid had the following properties; pH 4.9, specific gravity 1.112,viscosity 6.61 cps, surface tension 40 dynes/cm, stability, more than 2months.

The fluid was printed with a 15 inches wide laboratory rotogravureprinting unit at speeds up to 2,000 fpm on soft, absorbent 2-ply, drycrepe tissue, i.e., facial tissue. The paper had an attractive greendesign imprinted thereon, which print had a color transfer rating of 0after 4 weeks of aging.

EXAMPLE 54 33 parts by weight of 37 percent CH O solution were added to66 parts by weight of the above described (UFC-l 156) having a N.V.S. ofapproximately 29 percent. 0.75 parts by weight of the acid dye C.l. AcidBlue 45, Anthraquinone Blue BN, DuPont, and 0.2 parts by weight of thereactive dye Cibacron Turquoise Blue G-E, Ciba, were dissolved in theabove solution with agitation and heating to approximately 140F. Theresulting solution was agitated for 15 minutes and 1 part of glacialacetic acid catalyst was slowly added.

The fluid had the following properties: pH 4.9, specific gravity 1.107,viscosity 5.93 cps, surface tension 39.9 dynes/cm, stability -more than2 months.

The fluid was printed with a 15 inches wide laboratory rotogravureprinting unit at speeds up to 2,000 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive bluedesign imprinted thereon, which print had a color transfer rating of 1after 4 weeks of aging.

EXAMPLE 55 33 parts by weight of 37 percent CH O were added to 66 partsby weight of the above described resin (UFC-1 156) having a N.V.S. ofapproximately 29 percent. 0.018 parts by weight of the direct dye C.l.Direct Black 38, DuPont Fiber Black UF, and 1.5 parts by weight of thedirect dye C.l. Direct Yellow 54, Solantine Yellow 2RLL, National, weredissolved in the above solution with agitation and heating toapproximately 140F. The resulting solution was agitated for 15 minutesand 1 part glacial acetic acid catalyst was slowly added.

The fluid had the following properties: pH 4.9, specific gravity 1.1 13,viscosity 6.29 cps, surface tension 41.6 dynes/cm., stability betterthan 2 months.

The fluid was printed with a 15 inches wide laboratory rotogravureprinting unit at speeds up to 2,000 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive yellowdesign imprinted thereon, which print had a color transfer rating ofafter 4 weeks of aging.

EXAMPLE 56 0.90 parts by weight of a direct dye, C.l. Direct Red 76,Solantine Scarlet G (Allied Chemical) and 0.10 parts by weight of areactive dye Cibacron Yellow 3G, Ciba, were dissolved in 100 parts ofwater in a container, with agitation and heating to 130F. The resultingsolution was added slowly with agitation to 100 parts by weight of aresin solution prepared by taking 66 parts by weight of the abovedescribed resin (UFC- 1156), 33 parts by weight of 37 percent CH O and 1part acetic acid glacial. The resulting solution was agitated forminutes.

The fluid had the following properties: pH 5.4, specific gravity 1.054,surface tension 58.7, stability better than 2 months.

The fluid was printed with a 15 inches wide laboratory rotogravureprinting unit at speeds up to 2,000 fpm on soft, absorbent, 2-ply drycrepe paper, i.e., facial tissue. The red imprinted area had a transferrating of 0 after 4 weeks of aging at room temerature.

EXAMPLE 57 33 parts by weight of 37 percent CH O were added to 66 partsby weight of the resin described in Example 1 (UFC-1 156) having aN.V.S. of approximately 29 percent. 3.5 parts by weight of the reactivedye Cibacron Brilliant Yellow 36, CI. Reactive Yellow 2, Ciba, 0.5 partsby weight of the reactive dye, C.I. Reactive Blue 7, Cibacron TurquoiseBlue G, Ciba, were dissolved in the above solution with agitation andheating to approximately F. The resulting solution was agi tated for 15minutes and 1 part glacial acetic acid catalyst was slowly added.

The fluid had the following properties: pH -4.9, surface tension 38.9dynes/cm., stability better than 2 months.

The fluid was printed with a 15 inches wide laboratory rotogravureprinting unit at speeds up to 240 fpm on soft, absorbent, 2-ply drycrepe tissue, i.e., facial tissue. The paper had an attractive greendesign imprinted thereon, which print had a color transfer rating of 3after 4 weeks of aging.

EXAMPLE 58 66 parts by weight of the resin described in Example 1(UFC-1156), 29.14 percent N.V.S., was modified by addition of 33 partsby weight of 37 percent CH O solution, 1 part by weight of acetic acid(glacial). 2 parts by weight of Cl Direct Red 26, Pontamine Fast Scarlet3 BSN, were added and mixed with agitation and heating to 140F. untilsolution was homogeneous.

The fluid had the following properties: pH 4.9, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-p1y crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 59 66 parts by weight of resin previously described in Example 1of (UFC-1l56) approximately 29 percent N.V.S. was modified by additionof 33 parts by weight of 37 percent CH O solution, 1 part by weight ofacetic acid glacial. 2 parts by weight of CI. Direct Blue 15, PontamineSky Blue 5 BX, DuPont, were added and mixed with agitation and heatingto 140F until solution was homogeneous.

The fluid had the following properties: pH 4.9, stability above 3months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent 2-ply crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F 10F).

EXAMPLE 60 66 parts by weight of resin (UFC-l 156), previously describedin Example 1, 29 percent N.V.S., was modifled by addition of 33 parts byweight of 37 percent CH O solution, 1 part by weight of glacial aceticacid.

2 parts by weight of a direct dye, C.1. Direct Brown 95, ChlorantineFast Brown P-BRLL, were added directly to the modified resin solutiondescribed above with agitation and heat to 140F. The fluid was mixeduntil solution was complete.

The fluid had the following properties: pH 4.9, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply crepe paper, i.e., facial tissue. The brownimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F 10F).

EXAMPLE 61 66 parts by weight of resin (UFC-1156), previously describedin Example 1 of approximately 29 percent N.V.S., was modified byaddition of 33 parts by weight of 37 percent CH O solution, 1 part byweight of acetic acid (glacial). 0.83 parts by weight of CI. DirectYellow 50, Pontamine Fast Yellow RL, DuPont, and 0.17 parts by weight ofCl. Direct Brown 95, Pontamine Fast Brown NP, DuPont were added andmixed with agitation and heating to 140F until solution was homogeneous.

The fluid had the following properties: pH 4.7, stability 2 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply crepe paper, i.e., facial tissue. The goldenyellow imprinted area had a transfer rating of after 4 weeks of aging atroom temperature (77F i F).

EXAMPLE 62 66 parts by weight of resin (UFC-l 156), previously describedin Example 1 of approximately 29 percent N.V.S., was modified byaddition of 33 parts by weight of 37 percent CH O solution, and 1 partby weight of acetic acid (glacial). 1.96 parts by weight of CI. AcidBlue 127, Lanasyn Brilliant Blue GL, Sandoz, and 0.2 parts by weight ofCl. Direct Violet 9, Allied Chemical, Erie Brilliant Violet B conc. 200percent and 0.2 parts by weight of Direct Black 38, Pontamine Black ETP,DuPont, were added and mixed with agitation and heating to [40F untilthe solution was homogeneous.

The fluid had the following properties: pH 5.2., stability more than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 1 after 4 weeks of aging at roomtemperature (77F 1 10F).

EXAMPLE 63 1 part by weight of an acid dye, C.1. Acid Yellow 3,Schinoline Yellow 0 conc., Sandoz, was dissolved in 100 parts of waterin a container with agitation and heat to 140F. The resulting solutionwas added slowly with agitation to 100 parts by weight of resin solutionprepared as follows: 66 parts by weight of resin (UPC- 1 156),previously described in Example 1, 33 parts by weight of 37 percent CH Oand 1 part of glacial acetic acid, the solution having 29 percent N.V.S.The resulting solution was agitated for minutes.

The fluid had the following properties: pH 4.8, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The yellowimprinted area had a transfer rating of 2 after 4 weeks of natural agingat room temperature (77F i 10F).

EXAMPLE 64 1 part by weight of an acid dye, C.l. Acid Green 3, AcidGreen 2 G conc., Sandoz, was dissolved in 100 parts of water in acontainer with agitation and heat to 140F. The resulting solution wasadded slowly with agitation to 100 parts by weight of resin solutionprepared as follows: 66 parts by weight of the resin (UFC-l 156),described in Example 1, (29 percent N.V.S.), 33 parts of CH O (37percent solution) and 1 part of acetic acid (glacial). The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 4.8, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The greenimprinted area, had a transfer rating of 2 after 4 weeks of aging atroom temperature (77F i 10F).

EXAMPLE 65 1 part by weight of a direct dye, C.l. Direct Violet 47,DuPont, Pontamine Fast Violet 4RL, was dissolved in parts of water in acontainer with agitation and heat to 140F. The resulting solution wasadded slowly with agitation to 100 parts by weight of resin solutionprepared as follows: 66 parts by weight of the resin (UFC-l 156),described in Example 1, (29 percent N.V.S.), 33 parts of 37 percent CH Oand 1 part of glacial acetic acid. The resulting solution was agitatedfor 15 minutes.

The fluid had the following properties: pH 4.6, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The violetimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 66 1 part by weight of a reactive dye, Reactive Blue 5, CibacronBrilliant Blue BR, Ciba, was dissolved in 100 parts of water in acontainer with agitation and heating to 140F. The resulting solution wasadded slowly with agitation to 100 parts by weight of a resin solutionprepared as follows: 66 parts by weight of the resin (UFC- 1156),described in Example 1, (29 percent N.V.S.), 33 parts of CH O (37percent solution) and 1 part acetic acid (glacial). The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 4.5, stability 1 month.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The blueimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 67 1 part by weight of a reactive dye, Drimarine Red Z 28 CI.Reactive Red 17, Sandoz, was dissolved in 100 parts of water in acontainer with agitation and heating to F. The resulting solution wasadded slowly with agitation to 100 parts by weight of a resin solutionpre- I pared as follows: 66 parts by weight of the resin (UPC- 1 156),described in Example 1, (29 percent N.V.S. approximately), 33 parts ofCH O (37 percent solution) and 1 part acetic acid glacial. The resultingsolution was agitated for 15 minutes.

The fluid had the following properties: pH 4.8, stability 3 months.

The fluid was applied by a hand-operated simulated rotogravure method onsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 0 after 4 weeks of aging at roomtemperature (77F 10F).

EXAMPLE 68 1 part by weight of a direct dye, C.l. Direct Red 81,Pontamine Fast Red 8 BLX, DuPont, was dissolved in 100 parts of waterwith agitation and heating to 140F. The resulting solution was addedslowly with agitation to 100 parts by weight of a resin solutionprepared as follows: 66 parts by weight of the resin (UPC-1156),described in Example 1, (29 percent N.V.S.) 33 parts of CH O (37percent) and 1 part of acetic acid glacial. The resulting solution wasagitated for minutes.

The fluid had the following properties: pH 4.7, stability better than 2months.

The fluid was applied by a hand-operated simulated rotogravure methodonsoft, absorbent, 2-ply dry crepe paper, i.e., facial tissue. The redimprinted area had a transfer rating of 2 after 4 weeks of aging at roomtemperature (77F i 10F).

EXAMPLE 69 Twenty grams (0.177 mole) of e-caprolactam and 145 grams (1.0mole) of adipic acid were dissolved in a mixture of 93 grams (0.9 mole)of diethylene triamine, 20.0 grams (0.136 mole) of triethylene tetramineand 50 grams of water, and the resulting solution was heated in a vesselequipped with a mechanical agitator and condenser until the theoreticalamount of water was removed from the condensation product mixture. Thismixture was then heated to 195C to 210C for three and one-half hours,after which a vacuum was applied and heating was continued for anadditional half hour at 180C to 190C to insure that the condensationreaction was completed. The resulting product was cooled to about 140C,and then dissolved in 385 grams of water. The solution had a Gardnerviscosity of F at 25C and had a nonvolatile solids content ofapproximately 39.6 percent.

Ninety-one grams of this solution were added to 263 grams of water, andthe resulting solution was heated to 50C. Sixteen grams ofepichlorohydrin were added dropwise, and then the mixture was heated ata temperature of 65C to 70C until a Gardner viscosity of between D and Ewas obtained. One-hundred and fifty grams of water were added to quenchthe reaction and the product was cooled to room temperature. Thisproduct had a Gardner viscosity ofA at 25C, and contained approximately10 percent non-volatile solids.

A tenth of a gram of Pontamine Fast Blue 3RL dye was dissolved in 9.9grams of water, and this aqueous dye solution was then mixed with 10grams of the final resin product prepared above. The resulting printingfluid was stable for at least three days and when employed as a printingfluid for paper web material, resulted in a bleed-fast printed product.The following dyes can also be used in place of Pontamine Fast Blue 3RLto give equivalent results. Pontamine Fast Yellow RL, Pontamine FastRubine B, Pontamine Fast Green 2GL, Pontamine Deayo Orange 2R, andPonsol Direct Black 3GC.

EXAMPLE 70 One-hundred grams (1.0 mole) of adipic acid, 113 grams 1.09moles) of diethylene triamine and 50 grams of water were placed in a3-neck flask equipped with a mechanical stirrer, thermometer andcondenser, and the mixture was heated to 185C to 200C for one andthree-quarters hours. Heating was then discontinued, and a vacuum wasapplied until the reaction mixture cooled to 140C. At this point 215grams of water were then added. The resulting polyaminopolyamidesolution contained approximately 52.3 percent of nonvolatile solids.

Sixty-one and six-tenths grams of this solution were added to 16.0 gramsof a 37.5 percent solution of hydrochloric acid and 38.4 grams of water;10 grams of potassium cyanate were then added, and the resulting mixturewas heated to C to C for one hour. Thirty-three grams of a 37 percentformaldehyde solution were added to the mixture, and heating wascontinued until the reaction mixture became a viscous syrup. At thispoint, 20 grams of formaldehyde were added and stirring was continuedfor five additional minutes, to insure complete mixing of theformaldehyde into the resin syrup. The resulting solution wasneutralized to a pH of 7.0 with 10 percent sodium hydroxide and thendiluted with 25 grams of water. The final product containedapproximately 29 percent non-volatile solids.

A tenth of a gram of Pontamine Fast Turquoise 8 GLD was dissolved in 9.9grams of water, and this aqueous dye solution was then mixed with 10grams of the final resin product prepared above. The resulting printingfluid was stable for at least three days and, when employed as aprinting fluid for paper web material, resulted in a bleed-fast printedproduct. The following dyes can also be used in place of Pontamine FastTurquoise 8 GLD to give equivalent results: Pontamine Bond Yellow CR,Pontamine Fast Rubine B, Pontamine Deayo Green 3G, Pontamine Fast Orange6RN, Pontamine Brilliant Violet B, and Reactone Grey GL.

What is claimed is:

1. In the high speed rotogravure intaglio printing of a fibrous web, theimprovement which comprises utilizing, as the printing fluid therein, alow viscosity printing fluid comprising an aqueous solution of awatersoluble, cationic thermosetting resin and a watersoluble dyecompatible with said resin, said dye and resin mixture having astability of from about 1 hour to in excess of 4 months, a transferencevalue of from about 0 to about 4, and a viscosity of less than 20 cps.at 77F.

2. In the rotogravure intaglio printing of an absorbent fibrous web at avelocity up to and in excess of about 5,000 feet per minute, theimprovement which comprises utilizing, as the printing fluid therein, alow viscosity printing fluid comprising a non-dilatant, aqueous solutionof a water-soluble, cationic thermosetting resin and an anionic,transparent, water-soluble dye compatible with said resin, said solutionbeing free from particulate contamination and pigmented particles, andsaid dye and resin mixture having a stability of from about 1 hour to inexcess of 4 months, a transference value of from about 0 to about 4, aviscosity of less than 20 cps. at 77F., and a surface tension below thatof pure water.

3. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is prepared by reacting (a) a polybasic acid, (b) analkylene polyamine, and (c) a crosslinking agent.

4. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is prepared by reacting (a) a polybasic acid, (b) analkylene polyamine, (c) a glycol, and (d) epichlorohydrin.

5. The rotogravure intaglio printing process as defined by claim 3,wherein the resin is prepared by reacting an unsaturated polybasic acid,and is thereafter further reacted with an ethenoid compound.

6. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is prepared by reacting (a) urea, (b) an alkylenepolyamine, (c) formaldehyde and (d) at least one member of the groupconsisting of thiourea, dicyandiamide, guanadine and amino triazine.

7. The rotogravure intaglio printing process as defined by claim 6,wherein the resin is obtained by reacting urea, formaldehyde, diethylenetriamine and melamine.

8. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is prepared by reacting (a) urea, (b) formaldehyde,(c) an alkylene polyamine of the formula 2 m 2m .r wherein x is aninteger of l to 4 and m is an integer of 2 to 3, and (d) at least onemember of the group consisting of thiourea, dicyandiamide, guanidine andaminotriazine, in the presence of at least one compound of the classconsisting of paraformaldehyde, methyl alcohol, ethyl alcohol, propylalcohol, butyl alcohols, ethylene glycol, glycerine, diethylene glycols,triethylene glycols, glucose, furfuryl alcohol, dimethyl sulfoxide anddimethylformamide.

9. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is prepared by reacting (a) at least one polybasicacid of the formula HOOC R COOH where R is of from 2 to 16 carbon atomsand is selected from the group consisting of saturated aliphaticmoieties, unsaturated hydrocarbon moieties, alicyclic moieties, andaromatic moieties; (b) an alkylene polyamine of the formula 2 m 2m )p m21n 2 wherein Y is selected from the group consisting of H and C l-lNl-l and wherein m is an integer from 2 to 4 and p is an integer from 1to 4; (c) an alkylene glycol of the formula )rI( m 2m )u m 2m wherein gis an integer from O to 6 and m is an integer from 2 to 4; and (d) acrosslinking agent selected from the class consisting of halohydrins,diglycidylether and alpha, omega dihaloalkylenes; provided that when insaid polybasic acid R is an unsaturated moiety the condensate is furtherreacted with an ethenoid compound selected from the class consisting ofvinylacetate and lower alkyl esters of acrylic and methacrylic acids.

10. The rotogravure intaglio printing process as defined by claim 9,wherein the resin is prepared by reacting only components (a), (b) and(d).

11. The rotogravure intaglio printing process as defined by claim 9,wherein the resin is prepared by reacting only components (a), (b) and(d), and said polybasic acid moiety R is an unsaturated moiety.

12. The rotogravure intaglio printing process as defined by claim 10,wherein the polybasic acid is adipic acid, the alkylene polyamine isdiethylene tetramine and the cross-linking agent is epichlorohydrin.

13. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is a cationicureaformaldehyde resin condensate.

14. The rotogravure intaglio printing process as defined by claim 13,wherein the resin is an aminemodified urea-formaldehyde thermosettingresin condensate.

15. The rotogravure intaglio printing process as defined by claim 14,wherein the resin is prepared by the acid condensation of a reactionmixture of urea, formaldehyde and at least one polyalkylene polyamine ofthe formula z n 2n ).r H wherein x is an integer of l to 4 and n is 2 or3.

16. The rotogravure intaglio printing process as defined by claim 13,wherein the resin is prepared by the acid condensation of a reactionmixture of urea, formaldehyde, at least one polyalkylene polyamine ofthe formula HZN n 2n .r wherein x is an integer of l to 5 and n is 2 or3, and a viscosity lowering additive selected from the class consistingof formaldehyde, methyl alcohol, ethyl alcohol, normal propyl alcohol,isopropyl alcohol, tertiary-butyl alcohol, ethylene glycol, diethyleneglycol, triethylene glycol, glycerine, furfuryl alcoholdimethylformamide, and wherein additional amounts of the viscositylowering additive are added after each incipient gellation in order toenable the condensation reaction to be continued to the desired degreeof condensation.

17. The rotogravure intaglio printing process as defined by claim 2,wherein the resin is prepared by reacting:

a, a compound selected from at least one member of the group consistingof amino-carboxylic acids of the formula lactams of the formula whereinR is a divalent radical selected from the group consisting of saturatedand unsaturated carbon atom chains of from 2 to 20 carbon atoms,alicyclic radicals; and aromatic radicals; and R is an aliphatic chainof from 4 to 18 carbon atoms;

b. a compound selected from at least one member of the group consistingof dibasic acid of the formula HOOCR COOH wherein R is a divalentradical selected from the group consisting of saturated l to 20 carbonatom radicals, unsaturated 2 to 20 carbon atom radicals, alicyclicradicals, aromatic radicals, and the esters and anhydrides of theseacids; and

c. at least one polyalkylene polyamine compound of the formula H N(R"NH),.H wherein R is an alkylene group of from 2 to 8 atoms and n is aninteger of from about 1 to 5, provided that at least 50 percent of thepolyamine compound is where n is greater than one; the above (a), (b)and (c) components on mole basis in the reaction mixture being of fromabout 0.l:l.0: 0.9 to about l.0:l.0:l.3 respectively; the reaction beingcarried out at a temper-

1. IN THE HIGH SPEED ROTOGRAVURE INTALGIO PRINTING OF A FIBROUS WEB, THEIMPROVEMENT WHICH COMPRISES UTILIZING, AS THE PRINTING FLUID THEREIN, ALOW VISCOSITY PRINTING FLUID COMPRISING AN AQUEOUS SOLUTION OF AWATER-SOLUBLE, CATIONIC THERMOSETTING RESIN AND A WATER-SOLUBLE DYECOMPATIBLE WITH SAID RESIN, SAID DYE AND RESIN MIXTURE HAVING ASTABILITY OF FROM ABOUT 1 HOUR TO IN EXCESS OF 4 MONTHS, A TRANSFERENCEVALUE OF FROM ABOUT 0 TO ABOUT 4, AND A VISCOSITY OF LESS THAN 20 CPS.AT 77*F.
 2. In the rotogravure intaglio printing of an absorbent fibrousweb at a velocity up to and in excess of about 5,000 feet per minute,the improvement which comprises utilizing, as the printing fluidtherein, a low viscosity printing fluid comprising a non-dilatant,aqueous solution of a water-soluble, cationic thermosetting resin and ananionic, transparent, water-soluble dye compatible with said resin, saidsolution being free from particulate contamination and pigmentedparticles, and said dye and resin mixture having a stability of fromabout 1 hour to in excess of 4 months, a transference value of fromabout 0 to about 4, a viscosity of less than 20 cps. at 77*F., and asurface tension below that of pure water.
 3. The rotogravure intaglioprinting process as defined by claim 2, wherein the resin is prepared byreacting (a) a polybasic acid, (b) an alkylene polyamine, and (c) acrosslinking agent.
 4. The rotogravure intaglio printing process asdefined by claim 2, wherein the resin is prepared by reacting (a) apolybasic acid, (b) an alkylene polyamine, (c) a glycol, and (d)epichlorohydrin.
 5. The rotogravure intaglio printing process as definedby claim 3, wherein the resin is prepared by reacting an unsaturatedpolybasic acid, and is thereafter further reacted with an ethenoidcompound.
 6. The rotogravure intaglio printing process as defined byclaim 2, wherein the resin is prepared by reacting (a) urea, (b) analkylene polyamine, (c) formaldehyde and (d) at least one member of thegroup consisting of thiourea, dicyandiamide, guanadine and aminotriazine.
 7. The rotogravure intaglio printing process as defined byclaim 6, wherein the resin is obtained by reacting urea, formaldehyde,diethylene triamine and melamine.
 8. The rotogravure intaglio printingprocess as defined by claim 2, wherein the resin is prepared by reacting(a) urea, (b) formaldehyde, (c) an alkylene polyamine of the formulaH2N(CmH2mHN) xH wherein x is an integer of 1 to 4 and m is an integer of2 to 3, and (d) at least one member of the group consisting of thiourea,dicyandiamide, guanidine and aminotriazine, in the presence of at leastone compound of the class consisting of paraformaldehyde, methylalcohol, ethyl alcohol, propyl alcohol, butyl alcohols, ethylene glycol,glycerine, diethylene glycols, triethylene glycols, glucose, furfurylalcohol, dimethyl sulfoxide and dimethylformamide.
 9. The rotogravureintaglio printing process as defined by claim 2, wherein the resin isprepared by reacting (a) at least one polybasic acid of the formulaHOOC - R - COOH where R is of from 2 to 16 carbon atoms and is selectedfrom the group consisting of saturated aliphatic moieties, unsaturatedhydrocarbon moieties, alicyclic moieties, and aromatic moieties; (b) analkylene polyamine of the formula H2N(CmH2mNY)pCmH2mNH2 wherein Y isselected from the group consisting of H and CmH2mNH2 and wherein m is aninteger from 2 to 4 and p is an integer from 1 to 4; (c) an alkyleneglycol of the formula HO(CHOH)g(CmH2mO)gCmH2mOH wherein g is an integerfrom 0 to 6 and m is an integer from 2 to 4; and (d) a crosslinkingagent selected from the class consisting of halohydrins, diglycidyletherand alpha, omega dihaloalkylenes; provided that when in said polybasicacid R is an unsaturated moiety the condensate is further reacted withan ethenoid compound selected from the class consisting of vinylacetateand lower alkyl esters of acrylic and methacrylic acids.
 10. Therotogravure intaglio printing process as defined by claim 9, wherein theresin is prepared by reacting only components (a), (b) and (d).
 11. Therotogravure intaglio printing process as defined by claim 9, wherein theresin is prepared by reacting only components (a), (b) and (d), and saidpolybasic acid moiety R is an unsaturated moiety.
 12. The rotogravureintaglio printing process as defined by claim 10, wherein the polybasicacid is adipic acid, the alkylene polyamine is diethylene tetramine andthe cross-linking agent is epichlorohydrin.
 13. The rotogravure intaglioprinting process as defined by claim 2, wherein the resin is acationic-ureaformaldehyde resin condensate.
 14. The rotogravure intaglioprinting process as defined by claim 13, wherein the resin is anamine-modified urea-formaldehyde thermosetting resin condensate.
 15. Therotogravure intaglio printing process as defined by claim 14, whereinthe resin is prepared by the acid condensation of a reaction mixture ofurea, formaldehyde and at least one polyalkylene polyamine of theformula H2N (CnH2nHN)x H wherein x is an integer of 1 to 4 and n is 2 or3.
 16. The rotogravure intaglio printing process as defineD by claim 13,wherein the resin is prepared by the acid condensation of a reactionmixture of urea, formaldehyde, at least one polyalkylene polyamine ofthe formula H2N (CnH2nHN) xH wherein x is an integer of 1 to 5 and n is2 or 3, and a viscosity lowering additive selected from the classconsisting of formaldehyde, methyl alcohol, ethyl alcohol, normal propylalcohol, isopropyl alcohol, tertiary-butyl alcohol, ethylene glycol,diethylene glycol, triethylene glycol, glycerine, furfuryl alcoholdimethylformamide, and wherein additional amounts of the viscositylowering additive are added after each incipient gellation in order toenable the condensation reaction to be continued to the desired degreeof condensation.
 17. The rotogravure intaglio printing process asdefined by claim 2, wherein the resin is prepared by reacting: a. acompound selected from at least one member of the group consisting ofamino-carboxylic acids of the formula
 18. The rotogravure intaglioprinting process as defined by claim 17, wherein the resin is obtainedby reacting e-caprolactam, adipic acid, diethylene triamine andtriethylene tetramine and epichlorohydrin.
 19. The rotogravure intaglioprinting process as defined by claim 2, wherein the resin is prepared byreacting: a. at least one member of the group consisting of a saturatedaliphatic dicarboxylic acid having from 4 to 6 carbon atoms, diglycolicacid and dithioglycolic acid, with b. at least one member of the groupconsisting of a polyalkylene polyamine of the formula H2N(RNH)nH where Ris an alkylene group of 2 to 4 carbon atoms and n is An integer from 2to 5, said polyalkylene polyamine and said dicarboxylic acid beingreacted in a mole ratio of from about 0.9:1.0 to about 1.15:1.0 in anaqueous medium at a temperature of from about 160*C to about 210*C; c.converting by means of an inorganic acid the polyamino-polyamidereaction product from steps (a) and (b) to an inorganic acid saltthereof; d. reacting said salt with an alkali cyanate in an aqueoussolution to form a polyureide derivative, said cyanate being selectedfrom at least one member of the group consisting of lithium cyanate,sodium cyanate, potassium, thiocyanate, said alkali metal cyanate beingreacted with said polyaminopolyamide in mole ratios from about 0.8:1.2moles of the cyanate per mole of reactive amine, at a temperature offrom about 50*C to about 80*C; and e. reacting the preceding productwith an aldehyde selected from at least one member of the classconsisting of formaldehyde, paraformaldehyde and trioxane, said aldehydebeing present in an amount such that it is equivalent to from 1:1 toabout 3:1, at a temperature of from about 60*C to about 90*C.
 20. Therotogravure intaglio printing process as defined by claim 19, whereinthe resin is obtained by reacting adipic acid, diethylene, triamine,hydrochloric acid, potassium cyanate and formaldehyde.
 21. Therotogravure intaglio printing process as defined by claim 2, wherein thesaid printing fluid has a viscosity of less than 15 cps. at 77*F. 22.The rotogravure intaglio printing process as defined by claim 21,wherein the said printing fluid has a viscosity of between 3 and 10 cps.at 77*F.
 23. The rotogravure intaglio printing process as defined byclaim 22, wherein the said printing fluid has a viscosity of between 3and 7 cps. at 77*F.
 24. The rotogravure intaglio printing process asdefined by claim 2, wherein the said printing fluid has a surfacetension of from about 30 to about 60 dynes/cm.
 25. The rotogravureintaglio printing process as defined by claim 2, wherein the resin iscapable of thermosetting within at least four weeks.
 26. The rotogravureintaglio printing process as defined by claim 2, wherein the resin isself-curing.
 27. In a high speed rotogravure intaglio printingorganization, the improvement which comprises, as the printing fluidtherefor, a low viscosity printing fluid comprising a non-dilatant,aqueous solution of a water-soluble, cationic thermosetting resin and ananionic, transparent, water-soluble dye compatible with said resin, saidsolution being free from particulate contamination and pigmentedparticles, and said dye and resin mixture having a stability of fromabout 1 hour to in excess of four months, a transference value of fromabout 0 to about 4, a viscosity of less than 20 cps. at 77*F, and asurface tension below that of pure water.
 28. The rotogravure intaglioprinting process as defined by claim 2, wherein the absorbent fibrousweb printed is an unsized fibrous web.
 29. The rotogravure intaglioprinting process as defined by claim 2, wherein the absorbent fibrousweb printed is a cellulosic fibrous web.
 30. The rotogravure intaglioprinting process as defined by claim 29, wherein the cellulosic fibrousweb is selected from the group consisting of multi-ply toilet/facialtissue, single ply toilet tissue, single ply towel/wiper, multi-plytowel/wiper, single ply napkin and multi-ply napkin.